LIBRARY 

OF  THE 

UNIVERSITY  OF  CALIFORNIA. 

Class 


A  SHORT  HAND-BOOK 

HI  'Vv,-: '-  of 

OIL  ANALYSIS 


BY 

AUGUSTUS  H.  GILL,  S.B.,  Pn.D. 

AUTHOR  OF  '  '  GAS  AND  FUEL  ANALYSIS  FOR  ENGINEERS, "  "  ENGINE  ROOM  CHEMISTRY ' 

ASSOCIATE  PROFESSOR  OF  TECHNICAL  ANALYSIS  AT  THE  MASSACHUSETTS 

INSTITUTE  OF  TECHNOLOGY,  BOSTON,  MASS. 


FIFTH  EDITION 

REVISED    AND    ENLARGED 


OF  THE 

|   UNIVERSITY    ) 

OF 


PHILADELPHIA  AND  LONDON 

J.   B.   LIPPINCOTT    COMPANY 

1909 


! 


Copyright,  1897,  by  J.  B.  LIPPINCOTT  COMPANY. 


Copyright,  1900,  by  J.  B.  LIPPINCOTT  COMPANY. 


Copyright,  1903,  by  J.  B.  LIPPINCOTT  COMPANY. 


Copyright,  1905,  by  J.  B.  LIPPINCOTT  COMPANY. 


Copyright,  1909,  by  J.  B.  LIPPINCOTT  COMPANY. 


Electrotyped  and  Printed  by  J.  B.  Lippincott  Company 
The  Washington.  Square  Press,  Philadelphia,  U.  S.  A. 


vv 


PREFACE  TO  THE  FIFTH  EDITION. 

,  THE  changes  in  the  present  volume  include  a 
description  of  the  new  universal  viscosimeter, 
improved  methods  for  the  detection  of  antifluor- 
escents,  and  of  applying  the  spontaneous  combus- 
tion test.  The  portions  of  the  work  dealing  with 
the  detection  of  animal  and  vegetable  oils,  the 
treatment  of  unsaponifiable  matter,  and  the  tur- 
pentines have  been  entirely  rewritten.  A  new 
chapter  upon  waste  fats  and  oils  has  been  added 
in  view  of  their  increasing  importance.  Other 
additions  are  a  description  of  the  titer  test,  another 
method  for  sulphur  in  burning  oils,  and  some  new 
tables. 

As  in  the  past,  minor  changes  and  corrections 
have  been  made,  thus  bringing — it  is  hoped — the 
book  well  up  to  present  practice. 
BOSTON,  November,  1908. 


203801 


PREFACE  TO  THE  FIRST  EDITION. 

THIS  little  book  was  written  primarily  to  meet 
the  needs  of  the  author's  own  classes.  It  is  given 
to  the  public  in  the  belief  that  there  is  a  demand 
for  a  concise  manual  for  the  analysis  of  oils,  which 
shall  give  the  methods  of  applying  the  usual  physi- 
cal and  chemical  tests  to  the  mineral  as  well  as  to 
the  animal  and  vegetable  oils. 

It  is  not  designed  to  take  the  place  of  any  of  the 
existing  books,  but  rather  to  serve  as  an  introduc- 
tion to  them,  more  especially  to  Benedikt-Lewko- 
witsch,  which  is  to  the  oil  chemist  what  Fresenius 
is  to  the  analytical  chemist,  and  to  which  the  writer 
wishes  to  express  his  own  indebtedness.  The 
writings  of  Schaedler,  Redwood,  Allen,  and  Brannt 
have  also  been  freely  consulted.  Only  the  more 
commonly  occurring  oils  are  discussed,  and  these 
as  regards  their  preparation,  properties,  analytical 
constants, — the  highest,  lowest,  and  average  being 
given, — and  finally  their  uses  and  adulterants. 

In  the  use  of  this  book  it  is  assumed  that  the 
student  is  thoroughly  familiar  with  the  usual  opera- 
tions of  volumetric  and  gravimetric  analysis,  and 
has  attained  some  proficiency  in  organic  chemistry. 

Acknowledgments  are  due  to  Mrs.  Ellen  H. 
Richards  for  hints  and  suggestions,  and  to  Mr. 
William  L.  Root  for  assistance  in  reading  the  proof. 

BOSTON,  November,  1897. 

5 


CONTENTS. 


PART  I. 
PHYSICAL  AND  CHEMICAL  TESTS. 

CHAPTER  I. 

PETROLEUM    PRODUCTS. 

(a)  Burning  Oils. 

Flash  and  Fire  Tests — Specific  Gravity — Distillation  Test — 
Determination  of  Sulphur — Acidity — Sulphuric  Acid  Test 
—Test  for  Mineral  Salts— Water 13 

CHAPTER  II. 

PETROLEUM  PRODUCTS. 

(b)  Lubricating  Oils. 

Viscosity— Specific  Gravity — Evaporation — Cold — Flash  and 
Fire  Tests — Tests  for  Soap  and  Antifluorescents — Gum- 
ming Test— Friction  Tests 26 

CHAPTER  III. 

ANIMAL  AND   VEGETABLE  OILS. 

Specific  Gravity— Valenta — Elaidin— Maumene"  Test — Iodine 
Number — Bromine  Number — Saponification  Value — De- 
tection of  Unsaponifiable  Oils — Special  Tests — Free  Acid 
and  Spontaneous  Combustion  Tests — Drying  Test 49 

CHAPTER  IV. 

GENERAL  CONSIDERATIONS   REGARDING  LUBRICANTS. 

Method  of  Examination  of  an  Unknown  Oil..  86 


8  CONTENTS. 

PART  II. 

DERIVATION,  DESCRIPTION,  AND   EXAMINATION   OF 

CERTAIN  OILS. 
Classification 97 

CHAPTER  V. 

PETROLEUM   PRODUCTS. 

Naphthas — Gasolenes — Kerosenes — Lubricating  Oils 99 

A.  OILS  AND  FATS.     GLYCERIDES. 

CHAPTER  VI. 

VEGETABLE   OILS. 

(1)  Drying  Oils. 

Linseed,  Raw,  Boiled,  and  Bleached — Chinese  Wood — Poppy- 
seed — Sunflower 103 

(2)  Semi-Drying  Oils. 

Corn — Cotton-seed — Sesame — Rape-seed — Castor 108 

(3)  Non-Drying  Oils. 

Almond — Peanut — Olive — Rosin — Turpentine — Blown     Oils — 
Palm — Cocoanut 113 

CHAPTER  VII. 

ANIMAL  OILS. 

(1)  Marine  Animal  Oils. 

Menhaden— Cod— Whale 132 

(2)  Terrestrial  Animal  Oils. 
Neat's-foot— Horse— Lard—Tallow— Elaine 134 

B.   WAXES. 

LIQUID   WAXES. 

Sperm  Oil 139 

CHAPTER  VIII. 

WASTE   FATS. 

Wool    Fat— Distilled  Grease    Oleines— Sod    Oil— Oil  Foots— 
Fullers'  Grease— Black  Oil— Garbage  Grease 141 

APPENDIX. 
Tables— Reagents— -Railroad  Specifications 153 


PRELIMINARY  OBSERVATIONS. 

SAMPLES  of  oil  are  almost  always  handled  in  the 
trade,  and  frequently  brought  for  analysis,  in  a 
four-ounce  "oil  vial."  The  student  will  pour  out 
a  portion  from  the  quart  can,  after  thorough  shak- 
ing, into  such  a  vial.  Before  proceeding  with  the 
tests  to  be  later  described,  it  is  well  to  make  certain 
preliminary  observations  upon  this  sample. 

The  turbidity,  showing  the  presence  of  water  or 
of  oils  which  imperfectly  mix,  and  the  sediment, 
either  stearin  or  dirt,  are  to  be  noted;  the  color 
and  fluorescence,  or  "bloom," —  the  latter  indicating 
the  presence  of  mineral  oils, — are  next  observed;  the 
color  varies  from  "water  white,"  through  straw, 
lemon-yellow,  wine-red,  to  opaque. 

The  odor  and  taste  may  reveal  to  experts  much 
concerning  the  source  of  the  oil  under  examination; 
for  example,  the  fish  oils,  especially  when  warmed, 
have  an  unmistakable  odor,  and  the  presence  of 
whale  oil  in  sperm  is  often  detected  by  its  "nutty" 
taste. 

By  inverting  the  bottle  when  partially  filled,  and 
noting  the  way  in  which  the  oil  runs  off  from  the 
bottom  and  the  number  of  drops,  an  approximate 
idea  of  the  viscosity  may  be  obtained. 


PART  I. 
PHYSICAL  AND  CHEMICAL  TESTS. 


OP    THE 

UNIVERSITY 

OF 


A  SHORT   HAND-BOOK  OF 
OIL  ANALYSIS. 


CHAPTER  I. 
PETROLEUM  PRODUCTS. 

(a)  Burning  Oils. 

THE  tests  to  be  made  are,  in  the  order  of  their 
importance,  flash  test,  fire  test,  specific  gravity, 
distillation  test,  determination  of  sulphur,  acidity, 
sulphuric  acid  test,  test  for  mineral  salts,  deter- 
mination of  water. 

Flash  Test  or  Point.1 — By  flash  point  we  under- 
stand that  temperature  to  which  an  oil  must  be 
heated  to  give  off  vapors  which,  when  mixed  with 
air,  produce  an  explosive  mixture.  The  results  of 
this  test  will  vary  according  to  the  quantity  of  air 
over  the  surface  of  the  oil,  and  whether  this  be 
moving  or  still;  also  according  to  the  distance  of 
the  testing  flame  from  the  surface  of  the  oil.  Fur- 
thermore, the  size  of  the  flame,  the  length  of  its 
time  of  action,  its  form  and  dimensions,  and,  lastly, 

1  The  flash  point  is  oftentimes  a  valuable  means  of  detecting  the 
admixture  of  substances;  for  example,  0.1  per  cent,  ether  in  alco- 
hol may  be  discovered  by  this  test.  See  Table  II. 

13 


14  PHYSICAL  AND  CHEMICAL  TESTS. 

the  manner  of  heating  of  the  oil,  will  all  influence 
the  result.1 

From  the  above  statement  and  that  of  Dudley2 
the  following  points  are  to  be  especially  noted: 

1.  The   Rate  of  Heating. — The   faster  the   oil   is 
heated  the  lower  will  be  the  flash  point,  as  more 
vapor  is  driven  out. 

2.  Size  and  Depth  of  Cup. — From   a  large   and 
shallow  cup  the  liquid  evaporates  faster;  hence  the 
lower  will  be  the  flash  point.    The  most  constant  re- 
sults are  obtained  from  a  deep  cup  about  half  filled. 

3.  Quantity  of   Oil. — The   larger  the   amount   of 
oil  the  more  vapor  will  be  driven  out;  hence  the 
lower  will  be  the  flash  point. 

4.  Distance  of  Testing  Flame. — The  nearer  or — 
what  amounts  to  the  same  thing — the  larger  the 
testing  flame  the  lower  will  be  the  flash  point.     A 
large  flame  may  produce  local  superheating. 

5.  Point   of   Application  of   Testing  Flame. — The 
flame  should  be  applied  at  the  edge,  as  the  mixture 
of   air   and   vapor   is   more   complete;   this  is  best 
effected  by  drawing  the  flame  diametrically  across 
the  top  of  the  cup.    Dr.  Dudley  cites  an  instance  in 
which  the  flash  point  obtained  was  considerably  too 
high,  owing  to  the  fact  that  the  testing  flame  was 
first  applied  in  the  centre  of  the  cup. 

6.  The   thermometers   used   should   be   frequently 
compared  with  a  standard  instrument. 

7.  Draughts  should  be  carefully  avoided. 

1  Engler  and  Haa.se,  Z.  anal.  Chem.,  20,  3  (1881). 
'American  Engineer  and  Railroad  Journal,  64,  180  (1890). 


PETROLEUM  PRODUCTS.  15 

Numbers  1  to  4  may  be  briefly  summarized  as 
follows:  any  cause  producing  the  rapid  evolution 
of  a  large  amount  of  petroleum  vapor  tends  to  lower 
the  flash  point. 

Barometric  changes  are,  for  practical  work,  negli- 
gible, each  five  millimeters  between  seven  hundred 
and  forty-five  and  seven  hundred  and  seventy-five 
millimeters  causes  a  variation  of  but  0.1°  C. 

Lenz1  states  that  the  initial  temperature  of  the 
oil  is  of  importance,  and  as  a  result  of  several  hun- 
dred determinations  recommends  cooling  the  oil 
contained  in  the  flashing  cup  to  0°  C.  before  making 
the  test.  In  case  the  oil  contains  water,  it  must  be 
removed  by  treatment  with  calcium  chloride  or 
sulphate. 

The  apparatus  in  use  in  this  country  are  divided 
into  two  classes, — covered  testers,  in  which  the  cup 
is  covered  with  a  perforated  metal  or  glass  plate, 
and  open  testers,  in  which  the  cup  is  not  so  covered. 
In  the  author's  opinion  the  covered  testers  are  the 
more  scientific  and  give  the  more  concordant  re- 
sults, and  should  be  made  the  standard  instruments. 

Covered  Testers. — One  of  the  best  forms  of  testing 
apparatus  is  that  devised  by  the  Michigan  State 
Board  of  Health  in  1873,  modified  by  Dr.  A.  H. 
Elliott,  and  now  known  as  the  "New  York  State 
Board  of  Health  Tester,"  shown  in  Fig.  1. 

Description. — It  consists  of  a  copper  oil  cup, 
D,  holding  about  ten  ounces,  the  quantity  usually 

1 Z.  anal.  Chem.,  25,  265  (1886). 


16 


PHYSICAL  AND  CHEMICAL  TESTS. 


FIG.  1. 


contained  in  lamps,  heated  in  a  water-bath  by  a 
small  Bunsen  flame.  The  cup  is  provided  with  a 
glass  cover,  C,  carrying  a  thermometer,  B,  and  a 
hole  for  the  insertion  of  the  testing  flame, — a 
small  gas  flame  one-quarter  of  an  inch  in  length. 

Manipulation.  —  After 
describing  the  apparatus 
minutely,  the  regulations 
of  the  New  York  State 
Board  of  Health  say,1 "  (2) 
The  test  shall  be  applied 
according  to  the  following 
directions : 

"Remove  the  oil  cup 
and  fill  the  water-bath 
with  cold  water  up  to  the 
mark  on  the  inside.  Re- 
place the  oil  cup  and  pour 
in  enough  oil  to  fill  it  to 
within  one-eighth  of  an 
inch  of  the  flange  joining 
the  cup  and  the  vapor- 
chamber  above.  Care 
must  be  taken  that  the  oil 
does  not  flow  over  the  flange.  Remove  all  air- 
bubbles  with  a  piece  of  dry  paper.  Place  the  glass 
cover  on  the  oil  cup,  and  so  adjust  the  thermometer 
that  its  bulb  shall  be  just  covered  by  the  oil. 

"If  an  alcohol  lamp  be  employed  for  heating  the 


New  York  State  Board  of  Health 
tester. 


Report  of  the  New  York  State  Board  of  Health,  1882,  p.  495. 


PETROLEUM  PRODUCTS.  17 

water-bath,  the  wick  should  be  carefully  trimmed 
and  adjusted  to  a  small  flame.  A  small  Bunsen 
burner  may  be  used  in  place  of  the  lamp.  The 
rate  of  heating  should  be  about  two  degrees  per 
minute,  and  in  no  case  exceed  three  degrees. 

"As  a  flash  torch,  a  small  gas  jet  one-quarter  of 
an  inch  in  length  should  be  employed.  When  gas 
is  not  at  hand  employ  a  piece  of  waxed  linen  twine. 
The  flame  in  this  case,  however,  should  be  small. 

"When  the  temperature  of  the  oil  has  reached 
85°  F.  the  testings  should  commence.  To  this  end 
insert  the  torch  into  the  opening  in  the  cover, 
passing  it  in  at  such  an  angle  as  to  well  clear  the 
cover,  and  to  a  distance  about  half-way  between 
the  oil  and  the  cover.  The  motion  should  be  steady 
and  uniform,  rapid  and  without  any  pause.  This 
should  be  repeated  at  every  two  degrees'  rise  of  the 
thermometer  until  the  thermometer  has  reached 
95°,  when  the  lamp  should  be  removed  and  the 
testings  should  be  made  for  each  degree  of  temper- 
ature until  100°  is  reached.  After  this  the  lamp 
may  be  replaced  if  necessary  and  the  testings  con- 
tinued for  each  two  degrees. 

"The  appearance  of  a  slight  bluish  flame  shows 
that  the  flashing  point  has  been  reached. 

"In  every  case  note  the  temperature  of  the  oil 
before  introducing  the  torch.  The  flame  of  the 
torch  must  not  come  in  contact  with  the  oil. 

"The  water-bath  should  be  filled  with  cold  water 
for  each  separate  test,  and  the  oil  from  a  previous 
test  carefully  wiped  from  the  oil  cup." 

2 


18 


PHYSICAL  AND  CHEMICAL  TESTS. 


FIG.  2. 


Open  Testers.—  The  Massachusetts  statute  is  by 
no  means  as  definite  as  that  of  New  York;  the 
courts  have  decided  that  custom  fixes  the  method 
of  testing.  The  law  says/  "No  person  shall  offer 
for  sale.  .  .  illuminating  oils  made 
from  coal  or  petroleum  which  will 
evaporate  a  gas  under  100°  F.  [that 
is,  the  flashing  point  is  100°  F. — 
A.  H.  G.],  or  ignite  at  a  temper- 
ature of  less  than  110°  F.,  to  be 
ascertained  by  the  application  of 
Tagliabue's  or  some  other  approved 
instrument. " 

Manipulation. — Tagliabue's  open 
tester  (Fig.  2)  is  the  official  instru- 
ment. This  is  similar  to  the  pre- 
ceding, except  that  it  is  smaller, 
has  a  glass  oil  cup  and  no  cover. 
The  water-bath  is  filled  as  before, 
and  the  oil  cup  to  within  three- 
thirty-seconds  of  an  inch  of  the 
top.  The  heating  flame  is  adjusted 
so  that  it  is  three-fourths  of  an 
inch  high,  and  the  heating  pro- 
ceeded with  at  the  rate  of  two  and  a  half  degrees 
per  minute,  until  97°  F.  is  reached,  when  the  test 
flame  is  applied  and  the  testings  made  every  three 
degrees  until  the  flash  point  is  reached.  The  whole 
time  of  making  the  test  should  be  half  an  hour. 


Tagliabue's  open 
tester. 


Revised  Statutes  of  Massachusetts,  1902. 


PETROLEUM  PRODUCTS.  19 

Fire  Test. — The  fire  test  of  an  oil  is  the  temper- 
ature at  which  it  will  give  off  vapors  which  when 
ignited  will  burn  continuously.  It  is  made  by  con- 
tinuing to  heat  the  oil  (the  cover  being  removed 
in  the  case  of  a  closed  tester  without  slipping  out 
the  thermometer)  at  the  same  rate  after  the  flash 
test  is  made  and  noting  the  point  as  indicated 
above.  The  flame  is  extinguished  by  a  piece  of 
asbestos  board  and  the  heating  discontinued.  In 
the  case  of  many  illuminating  oils  this  point  is  from 
10°  to  20°  F.  higher  than  the  flash  point. 

Notes.-— In  the  case  of  "Mineral  Sperm"  (300° 
F.  fire  test  petroleum)  these  tests  should  be  made 
with  the  instrument  for  lubricating  oils  (page  41). 
The  heating  should  be  at  the  rate  of  15°  F.  per 
minute,  and  the  testing  flame  first  applied  at  230° 
F.,  and  then  every  seven  degrees  until  the  flashing 
point  is  reached. 

The  most  satisfactory  way  of  making  these  tests 
is  to  place  the  watch  upon  the  desk  and  read  the 
thermometer  at  the  expiration  of  every  minute,  not- 
ing each  reading  down  in  the  proper  column  in  the 
laboratory  note-book. 

Specific  Gravity.  —  This  is  usually  effected  by 
the  hydrometer;  a  hydrometer  jar  is  four-fifths 
filled  with  the  oil,  a  Baum6  hydrometer  introduced 
into  it,  and  the  depth  read  off  to  which  the  instru- 
ment sinks  in  the  oil.  This  may  be  effected  by 
placing  a  strip  of  white  paper  back  of  the  jar  and 
noting  the  point  at  which  the  lower  meniscus  of 
the  oil  touches  the  scale.  The  temperature  of  the 


20  PHYSICAL  AND  CHEMICAL  TESTS. 

oil  is  taken  at  the  same  time,  and  in  case  it  be  not 
60°  F.  (15.5°  C.),  for  every  increase  of  10°  F.  (5.5° 
C.)  subtract  1°  Baume  from  the  hydrometer  read- 
ing. The  specific  gravity  may  be  found  by  the 
formula  rl~m*>  B°  representing  the  reading  Baume 
at  15.5°  C. 

Notes.  —  Inaccurate  graduation  may  cause  an 
error  of  0.001,  but  if  the  instrument  be  carefully 
calibrated  it  is  accurate  to  0.0002.1  The  student 
will  make  this  test  upon  the  oil  at  the  ordinary 
temperature  and  correct  the  gravity  for  tempera- 
ture as  given  above.  In  practice  this  can  be  done 
by  Tagliabue's  "Manual  for  Inspectors  of  Coal 
Oil,"  which  gives  the  readings  at  60°  F.  for  any 
gravity  from  20°  to  100°  Baume,  between  20°  F. 
and  109°  F. 

Distillation  Test.  —  As  a  means  of  evaluating 
samples  of  kerosene,  Beilstein2  recommends  the 
fractional  distillation  of  two  hundred  cubic  centi- 
meters, using  a  tower.  As  the  method  of  Engler  is 
more  frequently  employed,  that  will  be  described. 

He  uses  a  peculiar  boiling  flask,  six  and  five-tenths 
centimeters  in  diameter,  with  neck  fifteen  centi- 
meters long,  and  with  the  side  tube  about  nine 
centimeters  from  the  springing  of  the  bulb;  this  is 
connected  with  a  Liebig  condenser  and  heated  by  a 
small  lamp  with  a  shield. 

Manipulation. — One  hundred  cubic  centimeters 
of  the  oil  are  measured  into  the  boiling  flask  and 

1  Wright,  J.  Soc.  Chem.  Ind.,  1 1,  302  (1892). 
3  Z.  anal.  Chem.,  22,  309  (1883). 


PETROLEUM  PRODUCTS.  21 

distilled  at  the  rate  of  two  to  two  and  five-tenths 
cubic,  centimeters  per  minute,  the  distillate  being 
caught  in  a  25  cc.  burette  or  graduate.  When  the 
distillation  is  to  be  broken,  the  lamp  should  be  taken 
away  and  the  temperature  allowed  to  sink  twenty 
degrees  and  again  brought  to  the  breaking  or  frac- 
tionating point,  as  long  as  any  considerable  quantity 
goes  over.  The  distillation  is  first  broken  at  150° 
C.,  and  then  each  fifty  degrees  until  290°  C.  is 
reached;  in  this  way  a  much  better  idea  of  the 
value  of  the  oil  is  obtained  than  if  the  distillation 
were  allowed  to  proceed  continuously  between 
these  points.  The  lighter  portions,  for  example, 
those  between  150°  and  200°,  burn  much  better 
than  those  between  250°  and  290°;  the  heavy 
portions  of  American  petroleum  burn  much  better 
than  those  of  the  Russian  oils. 

The  averages  from  four  samples  of  Caucasian 
and  ten  samples  of  American  oils  subjected  to  this 
test  were  as  follows,  in  per  cent,  by  volume:1 

Below  Above 

150°  C.  150°-290°C.  290°  C. 

Caucasian  petroleum 8.0  86.6  5.4 

American  petroleum 16.9  57.1  26.0 

Determination  of  Sulphur.  —  In  addition  to  the 
preceding  tests,  Professor  Peckham2  considers  the 
determination  of  sulphur  to  be  of  considerable  im- 
portance. The  deleterious  effect  of  the  oxides  of 
sulphur  upon  hangings  and  bindings  is  well  known, 
sulphuric  acid  being  their  ultimate  product.  The 

1  Veith,  "  Das  Erdoel,"  p.  244.       2  Report  upon  Petroleum. 


22  PHYSICAL  AND  CHEMICAL  TESTS. 

sulphur  exists  in  combination,  partly  as  compounds 
formed  from  the  sulphuric  acid  used  in  refining1 
and  partly  as  sulphides  already  formed  in  the  oil. 
-Its  qualitative  detection  may  be  effected  by  heating 
the  oil  to  its  boiling  point  with  a  bright  piece  of 
sodium  or  potassium.  If  sulphur  compounds  be 
present,  a  yellowish  layer  is  formed  upon  the  metal. 
After  cooling  add  distilled  water  drop  by  drop  until 
the  metal  is  dissolved,  and  test  for  sulphides  with 
sodium  nitro-prusside. 

For  the  quantitative  determination  of  sulphur 
many  methods  have  been  proposed.  Engler2  and 
Kissling3  burn  the  oil  in  an  apparatus  similar  to 
that  used  for  the  determination  of  sulphur  in  illumi- 
nating gas.  This  can  be  easily  made  from  a  small 
test-tube  three-eighths  of  an  inch  in  diameter  and 
two  and  three-eighths  inches  long,  fitted  with  a 
stopper  carrying  a  narrow  piece  of  tubing  through 
which  passes  a  piece  of  lamp-wicking  —  the  whole 
serving  as  a  small  lamp.  This  is  burned  under  a 
funnel  with  the  stem  bent  to  connect  with  two 
wash-bottles  containing  bromine  water  and  the 
products  of  the  combustion  of  the  oil  sucked 
through  these. 

The  lamp  is  partly  filled  with  the  oil  to  be  tested 
and  weighed,  burned  until  about  a  gram  of  oil 
has  been  consumed  and  again  weighed.  The  sulphuric 
acid  formed  in  the  bottles  containing  bromine  water 


l,  Dingier  's  pol.  J.,  216,  47  (1875). 
2  Chem.  Ztg.,  20,  197;  abstr.  J.  Soc.  Chem.  Ind.,  15,  383  (1896). 
8  Ibid.,  199;  abstr.  Analyst,  21,  162  (1896). 


PETROLEUM  PRODUCTS.  23 

is  determined  in  the  usual  way  with  barium  chloride. 

The  determination  should  of  course  be  made  in 
an  atmosphere  free  from  sulphur.  Aufrecht1  distils 
the  oil  with  sodium  bicarbonate,  which  takes  up* 
the  sulphur. 

Mabery2  states  that  for  oils  containing  more  than 
0.01  per  cent,  of  sulphur  the  well-known  method  of 
Carius — the  oxidation  in  a  sealed  tube  with  fuming 
nitric  acid — leaves  little  to  be  desired.  For  oils 
containing  a  smaller  percentage  than  this  he  employs 
a  modification  of  Sauer's  method — the  combustion 
of  the  oil  in  a  stream  of  air — and  subsequent  ab- 
sorption of  the  products  in  standard  sodium  hydrate. 
The  percentage  of  sulphur  should  not  exceed  0.05; 
Engler,  loc.  cit.,  and  Kissling3  found  0.02  to  0.03 
in  the  Pennsylvania,  and  0.04  to  0.05  in  the  Lima 
kerosenes. 

Detection  of  Acidity. — Shake  equal  quantities  of 
oil  and  warm  water  in  a  test-tube,  pour  off  the 
oil,  and  test  the  water  with  litmus  paper.  If  the 
water  be  strongly  acid,  the  quantity  may  be  deter- 
mined as  in  "Free  Acid,"  page  78. 

The  acid  in  this  case  is  most  probably  sulphuric, 
coming  from  the  refining  process. 

Sulphuric  Acid  Test.— The  object  of  this  test  is 
to  judge  of  the  degree  of  refinement  of  the  oil,  a 
perfectly  refined  oil  giving  little  or  no  color  when 
submitted  to  the  process.  One  hundred  grams 

1  Pharm.  Ztg.,41,  469;  abstr.  J.  Soc.  Chem.Ind.,  15,  680  (1896). 

2  Am.  Chem.  J.,  16,  544  (1894). 

3  Ch.  Rev.  d.  F.  &  H.  Ind.,  14,  157  (1906),  Anal.,  31,  342. 


24  PHYSICAL  AND  CHEMICAL  TESTS. 

of  oil  and  forty  grams  of  sulphuric  acid,  1.73  spe- 
cific gravity,  are  shaken  together  for  two  minutes 
in  a  glass-stoppered  bottle  and  the  color  of  the  acid 
noticed.  In  accurate  work  this  color  is  matched  by 
solutions  of  Bismarck  brown.1 

Mineral  Salts. — Salts  of  calcium  or  magnesium 
when  dissolved  in  the  oil  diminish  its  illuminating 
power;  their  action  is  to  form  a  crust  on  the  wick 
and  prevent  access  of  air. 

Redwood2  states  that  0.02  gram  of  either  of 
these  salts  in  one  thousand  grams  of  oil  diminishes 
the  illuminating  power  thirty  to  forty  per  cent, 
in  eight  hours. 

They  are  determined  by  distilling  one  hundred 
or  two  hundred  cubic  centimeters  of  the  oil  down  to 
about  twenty  cubic  centimeters,  evaporating  and 
igniting  this  residue,  and  subsequently  treating 
with  hydrochloric  acid.  The  calcium  and  mag- 
nesium are  then  determined  in  the  usual  way. 

Determination  of  Water.3  —  By  rubbing  the  oil 
together  with  a  little  eosin  on  a  glass  plate  the  oil 
will  take  on  a  pink  color  if  water  be  present.  Allen4 
states  that  water  in  oils  may  be  determined  by 
the  addition  of  a  weighed  amount  of  gently  ignited 
plaster  of  Paris.  This  is  washed  with  a  little  gaso- 
lene, dried  at  a  gentle  heat,  and  reweighed,  the 
gain  in  weight  being  the  water  present. 


1 J.  Soc.  Chem.  Ind.,  15,  678  (1896). 

*  Dingier  pol.  J.,  255,  427  (1887). 

3  See,  also,  Davis,  J.  Am.  Chem.  Soc.,  23,  487  (1901). 

*  Commercial  Organic  Analysis,  ii.  491. 


PETROLEUM  PRODUCTS.  25 

Another  method  of  determination  consists  in 
distilling  off  the  water  in  a  suitable  apparatus  and 
measuring  it  after  the  method  of  Dean  for  the 
determination  of  moisture  in  creosoted  wood.1 

It  is  to  be  noted  that  one  per  cent,  of  water  in  an 
oil  extinguishes  the  flame  when  making  the  flash 
test:  three  or  four  per  cent,  are  apparently  without 
influence  on  the  viscosity.2 

REFERENCES. 

In  addition  to  the  literature  previously  given,  the  student  is 
referred  to  the  following: 

ELLIOTT,  A.  H.,  New  York  State  Board  of  Health  Report,  1882, 
pp.  449-496.  This  gives  comparative  tests  of  the  various  testers 
and  a  resume  of  bibliography  and  patents  up  to  that  year. 

PECKHAM,  S.  F.,  "  Report  on  the  Production,  Technology,  and 
Uses  of  Petroleum  and  its  Products,"  U.  S.  Census  Report,  1885. 

THORNER,  W.,  Chemiker  Ztg.,  10,  528,  553,  573,  582,  601;  ab- 
stracted in  J.  Soc.  Chem.  Ind.,  5,  371  (1886).  "  Petroleum  as  an 
Illuminating  Agent." 

NEWBURY  and  CUTTER,  Am.  Chem.  J.,  10,  356  (1888).  "On  the 
Safety  of  Commercial  Kerosene  Oil." 

AISINMAN,  Chem.  technische  Vortrage,  ii.  325.  German  methods 
of  testing. 

1  Circular  134  (1908),  U.  S.  Dept.  Agriculture. 

2  Charitschkow,  Chem.  Ztg.,  31,  376  (1908). 


CHAPTER  II. 
PETROLEUM  PRODUCTS. 

(b)  Lubricating  Oils. 

THE  tests  to  be  made  are,  in  the  order  of  their 
importance,  viscosity,  specific  gravity^  evapora- 
tion, cold  test,  flash  test,  fire  test,  test  for  soap, 
test  for  antifluorescents,  friction  test. 

The  office  of  a  lubricant  is  to  prevent  the  attri- 
tion of  axle  and  journal  by  interposing  itself  be- 
tween them  in  a  thin  layer,  upon  which  the  shaft 
revolves.  The  ideal  lubricant  is  that  which  has 
the  greatest  adhesion  to  surfaces  and  the  least  cohe- 
sion among  its  own  particles,  or,  as  the  practical 
man  expresses  it,  the  most  fluid  oil  that  will  do  the 
work  and  stay  in  place.  The  determination  of  its 
viscosity  or  "body"  is  then  of  the  first  importance. 

Viscosity  is  the  degree  of  fluidity  of  an  oil  or  its 
internal  friction.  It  is  independent  of  the  specific 
gravity  of  the  oil,  although  this  in  the  pipette 
instruments  influences  the  time  of  efflux.  Within 
certain  limits  it  may  be  taken  as  a  measure  of  the 
value  of  oil  as  a  lubricant,  by  comparing  the  vis- 
cosity of  the  oil  under  examination  with  that  of 
other  oils  which  have  been  found  to  yield  good 
results  in  practice. 

The  instruments  employed  for  its  determination 
may  be  divided  into  two  classes, — pipette  viscosim- 

26 


LEUM  PRODUCTS.  27 


eters,  giving  the  time  of  efflux,  as  those  of  Saybolt, 
Engler,  and  others,  and  torsion  viscosimeters, 
giving  the  retardation  due  to  the  oil,  those  of  Napier 
and  Doolittle. 

Of  these  but  two,  the  Saybolt  and  Doolittle, 
will  be  minutely  described. 

The  Saybolt  Viscosimeter.1  —  This  is  made  in 
four  forms,  A,  B,  C,  and  the  Universal.  Apparatus 
"A"  is  the  standard  for  testing  at  70°  F.  Atlantic 
Red,  Paraffine,  and  other  distilled  oils;  "B"  for 
testing  at  70°  F.  Black  Oils  of  0°,  15°,  25°,  and 
30°,  Cold  Test,  and  other  reduced  oils  up  to,  but 
not  including,  Summer  Cold  Test  Oil.  Apparatus 
"C"  is  used  for  testing  at  212°  F.  Reduced,  Summer, 
Cylinder,  Filtered  Cylinder,  XXX  Valve,  26.5° 
Be.,  and  other  heavy  oils.  The  Standard  Universal 
Viscosimeter  is  used  for  testing  Cylinder,  Valve,  and 
similar  oils  at  210°  F.;  Reduced  Black  Oils  at  130°F.; 
Spindle,  Paraffine,  Red,  and  other  distilled  oils  at 
100°  F. 

Apparatus  "A."  —  Description.  —  The  "A"  appa- 
ratus (Fig.  3)  consists  of  a  brass  tube,  T,  containing 
about  sixty-six  cubic  centimeters,  and  about  three 
centimeters  in  diameter  and  eight  centimeters  long, 
forming  the  body  of  the  pipette.  It  is  connected 
at  the  bottom  with  a  smaller  tube,  t,  having  a  win- 
dow, w.  This  pipette  is  screwed  into  the  piece  p 
carrying  the  jet,  1.75  millimeters  in  diameter; 
the  lower  part  of  this  piece  is  expanded  at  the 

1  Redwood,  J.  Soc.  Chem.  Ind.,  5,  124  (1886). 


28 


PHYSICAL  AND  CHEMICAL  TESTS. 


FIG.  3. 


bottom  to  admit  of  the  insertion  of  a  cork.  The 
upper  part  of  the  pipette  is  perforated  with  a 
number  of  small  holes  leading  to  a  gallery,  G,  five 
centimeters  in  diameter  and  one  and  three-tenths 
centimeters  deep.  This  enables  a  workman  to  fill 
the  apparatus  to  the  same  point  every  time.  This 

pipette  is  held  by  p  in  a 
tank  of  water  eighteen  cen- 
timeters high  and  twenty 
centimeters  in  diameter, 
also  provided  with  win- 
dows to  observe  the  efflux 
of  the  oil. 

A  tin  cup  with  spout, 
thermometer,  pipette  with 
rubber  bulb,  stop-watch, 
and  beaker  for  waste  oil, 
complete  the  outfit. 

Manipulation. — H  a  v  i  n  g 
the  bath  of  water  prepared 
at  70°  and  the  oil  in  the  tin 
cup  about  69.5°,  clean  the 
tube  out  with  some  of  the 
oil  to  be  tested  by  using  the  plunger  sent  with  the 
instrument.  Place  the  cork  air-tight  in  the  lower 
outlet  tube  and  pour  the  oil  into  the  tube  proper 
until  it  flows  into  the  overflow  cup. 

By  stirring  with  the  thermometer  bring  the  oil 
to  exactly  70°,  remove  the  thermometer,  and  draw 
with  a  pipette  the  surplus  oil  in  the  overflow  cup 
down  below  the  overflow  holes.  The  temperature 


Saybolt's  "A"  viscosimeter. 


PETROLEUM  PRODUCTS.  29 

still  remaining  constant,  with  the  watch  in  the 
left  hand,  draw  the  cork  with  the  right  and  simul- 
taneously start  the  watch.  Towards  the  end  of 
the  run,  watch  the  peep-hole  closely  through 
the  window  in  the  bath,  and  at  the  first  appearance 
of  space  not  filled  with  oil  in  the  glass  outlet  tube 
stop  the  watch. 

Apparatus    "  C."— Standard  for  testing  at  212°  F. 

Description. — This  is  very  similar  to  the  preceding 
apparatus.  The  top  is  closed  around  the  oil  gallery, 
the  windows  omitted,  and  a  steam  connection  pro- 
vided. The  quantity  of  oil  is  determined  by  allowing 
it  to  run  into  a  sixty  cubic  centimeter  graduated 
flask.  The  size  of  the  jet  is  three-sixty-fourths  of 
an  inch.1 

Manipulation. — Fill  the  bath  with  water  and 
attach  steam  inlet  to  bottom  cock.  The  upper 
outlet  is  for  exhaust  and  overflow. 

With  the  water  boiling  and  the  bath  thermometer 
registering  212°,  and  the  oil  to  be  tested  having 
been  put  through  the  strainer  into  one  of  the  tin 
cups,  pour  some  of  the  oil  into  the  tube  and  clean 
out  with  the  plunger  sent  with  the  instrument; 
never  use  other  than  the  plunger  in  cleaning. 

Place  the  cork  air-tight  in  the  lower  outlet  tube, 
and  pour  the  oil  into  the  tube  until  it  overflows  into 
the  overflow  cup.  Allow  the  oil  to  heat  until  the 
temperature  is  210°,  stirring  the  oil  with  the  ther- 
mometer during  the  heating.  Having  the  bath  at 

^tillman,  J.  Anal,  and  App.  Chem.,  5,  322  (1891). 


30  PHYSICAL  AND  CHEMICAL  TESTS. 

212°  and  the  oil  not  below  210°,  remove  the  ther- 
mometer. Draw  the  surplus  oil  from  the  overflow 
cup  with  a  pipette  down  to  and  below  the  overflow 
holes;  this  insures  a  positive  starting-point. 

Place  the  sixty  cubic  centimeter  flask  under  and 
directly  in  a  line  with  the  outlet  jet,  and  as  close  to 
the  jet  as  it  is  practicable,  to  permit  of  room  for 
drawing  the  cork.  With  the  watch  in  the  left  hand, 
draw  the  cork  with  the  right  and  simultaneously 
start  the  watch.  The  time  required  for  the  delivery 
of  sixty  cubic  centimeters  is  the  viscosity.  The 
tube  should  be  cleaned  out  before  each  test  with 
some  of  the  oil  to  be  tested. 

Notes. — Instead  of  timing  the  oil  as  given  in  the 
directions  above,  the  writer  has  found  it  better  to 
start  the  watch,  and  the  instant  the  second-hand 
crosses  the  sixty  seconds  mark  twist  out  the  cork 
with  the  right  hand. 

The  tube  should  be  cleaned  out  before  each  test 
with  some  of  the  oil  to  be  tested,  using  the  plunger 
P  for  this  purpose.  Black  oils  or  any  oil  contain- 
ing sediment  should  be  carefully  strained  before 
testing  or  "  running, "  as  it  is  technically  termed. 
The  instruments  should  be  carefully  guarded  from 
dust  when  not  in  use. 

The  Universal  Viscosimeter. — Description. — This 
is  similar  to  Apparatus  C,  just  described:  in 
addition  to  the  steam  connection  it  is  provided 
with  a  ring  burner  for  heating  by  gas.  Sixty  cubic 
centimeters  of  oil  are  run  through  it  as  with  the 
preceding  instrument. 


PETROLEUM  PRODUCTS.  31 

It  may  be  used  for  testing  Cylinder,  Valve,  and 
similar  oils  with  bath  at  212°  and  oil  at  210°;  for 
testing  Reduced,  Black  Oils,  bath  and  oil  at  130°; 
for  testing  Spindle,  Paraffine,  Red,  and  other  dis- 
tilled oils,  batl^  and  oil  at  100°.  When  used  for 
testing  at  212°  F.,  it  may  be  used  with  either  gas 
or  steam  alone  or  both  in  combination.  If  with 
both,  the  steam  may  be  introduced  slowly,  more 
for  its  condensation  to  replace  evaporation  than 
for  real  heating  purposes,  depending  upon  the 
gas  flame  to  reach  the  boiling  point,  and  keeping 
it  there  during  the  operation  of  test.  The  bath 
vessel  should  always  be  kept  full  during  a  test, 
whether  at  212°,  130°,  or  100°.  When  used  at 
130°  or  100°,  gas  alone  is  used  to  bring  the  bath  to 
the  prescribed  temperature,  and  turned  off  during  the 
operation  of  test,  the  large  size  of  the  bath  usually 
permitting  making  one  test  without  reheating. 

Manipulation. 

1.  Have  the  bath  of  water  prepared  at  the  pre- 
scribed temperature. 

2.  Have  the  oil  strained  into  one  of  the  tin  cups, 
in  which  cup  it  may  be  heated  up  to  about  the 
standard  temperature. 

3.  Clean  out  the  tube  with  some  of  the  oil  to 
be  tested  by  using  the  plunger  sent  with  the  in- 
strument. 

4.  Place  the  cork  (as  little  distance  as  possible) 
into  the  lower  outlet  coupling  tube  just  enough  to 
make  air-tight,  but  not  far  enough  to  nearly  touch 


32  PHYSICAL  AND  CHEMICAL  TESTS. 

the  small  outlet  jet  of  the  tube  proper  (one-eighth 
to  one-quarter  of  an  inch  may  be  enough.) 

5.  Pour  the  oil  from  the  tin  cup  (again  through 
the  strainer)  into  the  tube  proper  until  it  overflows 
into  the  overflow  cup  up  to  and  above  the  upper 
edge  of  tube  proper. 

6.  Now  again  see  that  the  bath  is  at  the  pre- 
scribed temperature. 

7.  Use  the  thermometer  sent  with  the  instrument 
by  stirring  to  bring  the  oil  just  to  the  standard 
temperature. 

8.  Remove  the  thermometer. 

9.  Draw  from  the  overflow  cup,  with  a  pipette, 
all  the   surplus  oil  down  to  and    below  the  upper 
edge  of  tube  proper.     This  insures  a  positive  start- 
ing head. 

10.  Place   the   60   cc.    flask    under  and    directly 
in  line  with  the  outlet  jet,  and  as  close  to  the  coup- 
ling tube   as   is   practical   to   permit   of   room   for 
drawing   the    cork. 

11.  With  the  watch  in  left  hand  draw  the  cork 
with  the  right,  and  simultaneously  start  the  watch. 

12.  The  time  required  in  the  delivery  of  60  cc. 
is  the  viscosity. 

13.  Clean  out  the  tube  proper  before  each  test 
with  some  of  the  oil  to  be  tested. 

14.  No    drill    or    other    instrument    should    ever 
be  used  in  the  small  outlet  jet  of  tube  proper. 

The  results  obtained  with  this  instrument  are 
not  the  same  in  many  cases  as  those  furnished  by 
the  A,  B,  and  C  instruments,  nor  do  they  seem 


PETROLEUM  PRODUCTS. 


33 


FIG.  4. 


to  have  been  adopted  by  the  trade  generally. 
Tables  V-VIII  of  the  appendix  will  give  a  means 
of  comparing  the  results  obtained  with  the 
Saybolt,  Doolittle,  and  Engler  Viscosimeters. 

It  is  worth  noting  that  three  or  four  per  cent, 
of    water    are    apparently    without 
influence  on  the  viscosity. 

Doolittle's  Torsion  Viscosimeter.1 
— Description. — The  apparatus  con- 
sists of  a  cylinder  (Fig.  4)  rotating 
in  the  oil,  and  a  graduated  disk,  Z>, 
to  measure  the  amplitude  of  rota- 
tion. These  are  supported  by  a 
fine  piano  wire  from  the  substantial 
stand  S,  provided  with  levelling 
screws;  a  lens,  Z,  enables  the  gradu- 
ations on  the  disk  to  be  read  more 
accurately,  and  a  bath,  J5,  filled  with 
water  or  oil  serves  to  maintain  any 
desired  temperature.  The  instru- 
ment should  be  so  adjusted  that  it 
will  read  within  one-half  degree  of 
the  zero  point  on  either  side  of  it  when  vibrating 
through  an  arc  of  one  hundred  and  eighty  degrees; 
this  can  be  effected  by  loosening  the  set  screw  at 
the  top  and  turning  the  pin  which  holds  the  wire. 

Manipulation. — Immerse  the  friction  cylinder  in 
the  oil  by  slipping  its  stem  into  the  stem  of  the 
disk,  and  adjust  the  temperature  very  carefully  to 


Doolittle's  torsion 
viscosimeter. 


Doolittle,  J.  Am.  Chem.  Soc.,  15,  173,  454  (1893). 


34  PHYSICAL  AND  CHEMICAL  TESTS. 

the  point  at  which  it  is  desired  to  determine  the 
viscosity;  great  care  must  be  taken  to  keep  this 
temperature  constant  during  the  test.  Either  a 
water-bath  or  bath  of  lard  oil — according  to  the 
temperature  desired — may  be  used.  The  oil  in 
the  cup  should  cover  the  cylinder  with  a  layer 
three -sixteenths  of  an  inch  deep  when  it  is 
swinging  freely,  and  it  should  be  in  the  centre 
of  the  cup. 

By  lifting  the  milled  head  at  the  top  of  the  in- 
strument out  of  the  notch,  and  turning  it  completely 
around  from  right  to  left  until  it  drops  into  the 
notch  again,  the  wire  is  rotated  three  hundred  and 
sixty  degrees.  By  raising  the  disk  by  means  of  the 
cam  the  friction  cylinder  will  rotate  in  the  oil  by 
virtue  of  the  torsion  of  the  wire.  The  disk  will 
rotate  three  hundred  and  sixty  degrees  and  a  por- 
tion of  another  arc,  which  latter  is  the  first  reading, 
— the  end  of  the  first  swing  =  355.6°  right.  The 
left-hand  swing  is  ignored,  and  the  arc  on  the  next 
swing  to  the  right  =  338.2°  right,  is  read.  The 
retardation  produced  by  the  oil  is  355.6° — 338.2°  = 
17.4°.  The  vibrations  should  now  be  stopped, 
and  the  head  should  be  turned  in  the  opposite 
direction  and  the  readings  to  the  left  taken,  and 
the  average  of  the  two  considered  as  the  retarda- 
tion of  the  oil. 

The  results  are  expressed  in  the  number  of 
grams  of  sugar  contained  in  one  hundred  cubic 
centimeters  of  sugar  syrup  at  60°  F.,  its  viscosity 
being  taken  at  a  temperature  of  80°  F.  In  the  ex- 


PETROLEUM  PRODUCTS.  35 

ample  cited,  17.4°  (with  the  small  cylinder)  repre- 
sents a  viscosity  of  65.6;  this  means  that  if 
65.6  grams  of  granulated  sugar  were  dissolved  in 
water  at  60°  F.,  made  up  to  one  hundred  cubic 
centimeters  and  then  heated  to  80°  F.,  its  vis- 
cosity would  be  the  same  as  that  of  the  oil  under 
examination. 

The  readings  of  the  first  and  second  swings  are 
to  be  taken,  as  later  vibrations  give  different 
results.  The  wire  and  cylinder  should  be  handled 
with  great  care,  as  they  are  very  sensitive  to  abuse. 
The  wire  should  be  greased  with  tallow  occasion- 
ally, and  in  case  of  a  new  instrument,  restandard- 
ized  after  six  months'  use.  In  case  a  new  wire  is 
inserted  the  instrument  must  be  recalibrated. 
When  not  in  use  the  0°  point  should  be  kept  under 
the  index,  the  disk  upon  its  supports,  and  the  wire 
without  torsion. 

Traube's  Viscosimeter.— Dr.  T.  Traube,1  of  Han- 
over, uses  a  pipette  viscosimeter  consisting  of  a 
vertical  bulb  with  a  long  horizontal  capillary  jet, 
it  being  contained  in  a  trough  to  keep  the  tempera- 
ture constant.  About  eight  cubic  centimeters  of 
oil  are  used  for  a  test,  and  forced  through  the  jet 
under  a  pressure  of  sixty  centimeters  of  water. 
This  jet  is  thirty  centimeters  long  and  of  various 
diameters,  there  being  three  pipettes  with  jets 
1.5,  0.8,  and  0.5  millimeters  in  diameter,  according 
to  the  kind  of  oil  to  be  tested. 

Traube,  Z.  Ver.  deutsch.  Ing.,  31,  251;  abstr.  J.  Soc.  Chem. 
Ind.,  6,  414  (1887). 


36  PHYSICAL  AND  CHEMICAL  TESTS. 

Wright1  states  that  the  results  correspond  more 
closely  to  those  obtained  on  a  friction  machine 
than  those  of  any  other  instrument, — a  statement 
which  the  author's  experiments  would  seem  to 
confirm.  The  instrument  certainly  is  more  sensi- 
tive than  any  with  which  the  author  is  acquainted. 

Specific  Gravity. — 1.  By  the  Hydrometer.  See 
page  19. 

2.  By  the  Westphal  Balance. — This  is  a  specially 
constructed  instrument  with  a  glass  plummet 
carrying  a  thermometer  counterbalanced  by  a 
weight.  Upon  immersing  the  plummet  in  a  liquid 
the  positions  of  weights,  which  must  be  added  to 
restore  the  equilibrium,  represent  the  specific  grav- 
ity directly.  The  largest  weight  represents  the 
first  decimal  place,  the  next  the  second,  and  so  on. 
The  instrument  is  placed  upon  a  level  table,  and 
by  means  of  the  levelling  screw  is  brought  into  ad- 
justment,— i.e.,  so  that  the  point  upon  the  beam 
is  exactly  opposite  the  point  upon  the  fixed  part. 

The  plummet  is  now  placed  in  the  vial  or  balance 
jar  containing  the  oil,  cooled  to  15.5°  C.,  hung 
upon  the  balance,  being  careful  to  completely 
immerse  it  in  the  oil,  weights  added  to  restore  the 
equilibrium,  and  the  specific  gravity  read  off  as 
above  described. 

Notes. — In  using  the  instrument  care  should  be 
taken  to  place  the  riders  at  right  angles  to  the 

1  Oils,  Fats,  and  Waxes,  p.  109. 

For  the  absolute  viscosimeter,  see  "Lubrication  and  Lubri- 
cants, "  Archbutt  and  Deeley,  pp.  132-143. 


PETROLEUM  PRODUCTS.  37 

beam,  otherwise  an  error  of  0.0005  may  be  intro- 
duced; furthermore,  the  loop  upon  the  knife-edge 
should  always  be  in  the  same  position.  In  buying 
an  instrument  the  spaces  upon  the  beam  should  be 
tested  with  dividers  to  insure  their  equality,  other- 
wise serious  errors  may  be  caused.1  The  limit  of 
accuracy  is  about  0.0005.2 

Care  should  also  be  taken  that  the  plummet  does 
not  touch  the  sides  of  the  jar  or  vial. 

For  solid  fats  and  some  oils  the  specific  gravity 
is  taken  at  100°  C.,  using  a  special  plummet. 

McGill3  states  that  the  balance  is  more  sensitive 
for  viscous  oils  when  the  specific  gravity  of  the 
plummet  is  4.0  than  when  it  is  2.0. 

Evaporation  Test.4 — The  object  of  this  test  is  to 
determine  what  percentage  of  an  oil — more  espe- 
cially a  spindle  oil — is  volatile  when  exposed  to 
nearly  the  same  conditions  as  it  is  on  a  bearing. 

The  oil  is  exposed  upon  annular  disks  of  filter- 
paper  one  and  five-eighths  inches  outside  diameter, 
with  hole  five-eighths  of  an  inch  in  diameter, 
which  have  been  standing  in  a  sulphuric  acid 
desiccator  for  several  days,  contained  in  a  flat 
watch-glass. 

Manipulation. — The  watch-glass  and  paper  are 
weighed, — to  tenths  of  a  milligram, — and  about 
0.2  gram  of  oil  brought  upon  it-  by  dropping  from 


1  Allen,  Analyst,  14,  11;  Stock,  ibid.,  50  (1889). 

2  Richmond,  ibid.,  65. 

3  Analyst,  21,  156  (1896). 

4  See,  also,  Archbutt,  J.  Soc.  Chem.  Ind.,  15,  326  (1896). 


38  PHYSICAL  AND  CHEMICAL  TESTS. 

a  rod,  and  accurately  weighed.  The  watch-glass 
is  now  placed  in  an  air-bath,  the  temperature  of 
which  remains  nearly  constant  at  60°  to  65°  C. 
(140°  to  150°  F.),  and  heated  for  eight  hours.  It  is 
then  cooled  and  reweighed,  the  loss  being  figured 
in  per  cent.  No  oil  should  be  passed  which  gives 
an  evaporation  of  more  than  four  per  cent. 

The  following  table  of  results  upon  some  spindle 
oils  shows  the  relation  of  gravity,  flash  point,  and 
evaporation: 

Gravity.  Flash,  °F.  Evaporation. 

298  7.0  per  cent. 

.846  318  4.4 

348  2.0 

.852  348  1.0 

.856  336  1.4 

.862  352  0.9 

.866  366  1.7 

.870  384  0.8 

.882  364  1.7 

Notes.  —  The  temperature  employed,  65°  C.,  is 
approximately  that  attained  by  a  bearing  (in  a  spin- 
ning frame)  after  running  two  hours,  thus  leaving 
the  oil  exposed  to  it  for  eight  hours,  assuming  a  ten- 
hour  day. 

The  test  is  important  to  the  insurance  under- 
writer, because  it  measures  the  amount  of  inflam- 
mable material  sent  into  the  air,  and  hence  the 
liability  to  cause  or  aid  conflagrations;  it  is  impor- 
tant to  the  mill-owner,  as  it  indicates  the  quantity 
of  oil  left  upon  the  bearing,  hence  serving  its  purpose. 

Cold  Test. — This  may  be  defined  as  the  tempera- 
ture at  which  the  oil  will  just  flow. 


PETROLEUM  PRODUCTS.  39 

Manipulation.  —  A  four-ounce  vial  is  one-fourth 
filled  with  the  oil  to  be  examined,  a  short,  rather 
heavy,  thermometer  inserted  in  it,  and  the  whole 
placed  in  a  freezing  mixture.  When  the  oil  has  be* 
come  solid  throughout,  let  it  stand  one  hour;  the  vial 
is  removed,  the  oil  allowed  to  soften,  and  thoroughly 
stirred  until  it  will  run  from  one  end  of  the  bottle 
to  the  other.  The  reading  of  the  thermometer  is 
now  taken  by  withdrawing  it  and  wiping  off  the  oil 
with  waste  to  render  the  mercury  visible.1 

The  chilling  point  is  the  temperature  at  which 
flakes  or  scales  begin  to  form  in  the  liquid,  and  is 
determined  similarly,  by  cooling  the  liquid  five 
degrees  at  a  time. 

Freezing  Mixtures.  —  For  temperatures  above 
35°  F.  use  cracked  ice  and  water;  between  35°  and 
0°  F.  use  two  parts  of  ice  and  one  part  of  salt; 
and  from  0°  to  — 30°  F.  use  three  parts  of  crystal- 
lized calcium  chloride  and  two  parts  of  fine  ice  or 
snow.  A  still  more  convenient  means  is  by  the 
use  of  solid  carbonic  acid  dissolved  in  ether,  giving 
—50°  F.  readily. 

The  preceding  method  is  open  to  quite  an  error 
from  the  personal  equation  of  each  observer.  To 
obviate  this  Martens2  proceeds  as  follows: 

The  oil  is  poured  into  a  U-tube  one  centimeter 
in  diameter,  sixteen  centimeters  high,  with  three 
centimeters  between  the  bends,  to  a  depth  of  three 

1  Dudley  and  Pease,  Am.  Eng.  and  R.  R.  J.,  69,  332  (1895). 

2  Mitt.  kgl.  tech.  Versuchstation;  abstr.  J.  Soc.  Chem.  Ind.,  9, 
772  (1890). 


40  PHYSICAL  AND  CHEMICAL  TESTS. 

centimeters;  it  is  then  placed  in  a  freezing  mix- 
ture, cooled,  and  connected  with  a  blast  at  a  con- 
stant pressure  of  three  centimeters.  The  temper- 
ature at  which  the  oil  begins  to  flow  under  these 
conditions  is  considered  as  the  cold  test. 

Flash  Point. — Several  forms  of  apparatus  for 
testing  the  flash  point  of  lubricating  oils  have  been 
devised:  Pensky-Martens's  closed  tester  employing 
a  stirrer  is  used  in  Germany.  Martens  states  in  a 
later  article  that  stirring  is  unnecessary.  In  this 
country  an  open  cast-iron  or  spun  brass  cup  If 
inches  high  by  2J  inches  in  diameter  heated  by  a 
Tirrill  burner  in  an  air-bath  is  quite  extensively 
used.  Dudley  and  Pease  use  an  open  porcelain 
dish  heated  with  a  Bunsen  burner. 

Description. — The  apparatus  in  use  in  the  author's 
laboratory  is  similar  to  the  New  York  State  tester, 
and  consists  of  a  covered  copper  cup — shown  at 
about  one-tenth  the  size  in  Fig.  5 — supported  by 
iron  wire  gauze  upon  an  iron  stand  and  heated  by 
a  Tirrill  burner. 

Manipulation.  —  The  cup  is  filled  with  oil  to 
within  three-eighths  of  an  inch  of  the  flange  (in 
case  of  cylinder  or  oils  flashing  above  500°  one- 
half  inch),  all  air-bubbles  removed,  the  flange 
and  top  of  cup  carefully  wiped  free  of  oil,  the  cover 
put  on,  and  the  thermometer  inserted  so  that  its 
bulb  is  half-way  between  the  surface  of  the  oil 
and  bottom  of  the  cup.  The  lamp  is  placed  under- 
neath, carrying  a  flame  about  an  inch  in  height, 
the  bottom  of  the  cup  being  two  and  a  half  inches 


PETROLEUM  PRODUCTS. 


41 


from  the  mouth  of  the  burner,  and  the  heating 
commenced.  The  rate  of  heating  should  be  15° 
F.  per  minute,  and  may  be  readily  regulated  by 
the  burner  used.  The  testing  flame  should  be 
first  applied  at  250°  F.,  and  then  every  half-minute 

FIG.  5. 


Flash  apparatus. 

until  the  flash  point  is  reached.  This  is  indicated 
by  a  slight  puff  of  flame  out  of  the  testing  hole. 

Fire  Test.  —  The  cover  is  supported  above  the 
cup,  and  the  heating  and  application  of  the  testing 
flame  continued  as  in  making  the  flash  test. 

The  method  of  recording  is  the  same  as  in  the 
case  of  the  illuminating  oils,  one  column  for  times 


42  PHYSICAL  AND  CHEMICAL  TESTS. 

and  another  for  temperatures;  the  student  is 
recommended  to  read  again  pages  13-19.  Holde1 
finds  that  with  oils  flashing  between  172°  C.  and 
241°  C.  the  exact  quantity  of  oil  used  is  of  little 
importance.  In  these  particular  cases  a  difference 
of  filling  of  thirteen  cubic  centimeters  altered  the 
flash  point  only  1-1.5°  C.  For  the  effect  of  water 
see  p.  25. 

It  is  worthy  of  notice  that  the  free  acid  contained 
in  an  oil  lowers  its  flash  point  apparently  in  pro- 
portion to  the  quantity  present. 

Detection  of  Soap.  —  To  increase  the  viscosity 
of  an  oil,2  resort  is  had  to  the  use  of  "oil  pulp/' 
"  oil-thickener/7  or  "  white  gelatin/'  usually  an 
oleate  of  aluminium,  though  other  bases  may  be 
present.  Its  disadvantages  are  that  it  causes  the 
oil  to  chill  more  easily  and  to  emulsify,  thus  increas- 
ing the  friction.  Furthermore,  it  is  precipitated  by 
contact  with  water  or  steam,  causing  clogging  of 
the  machinery. 

The  test  depends  upon  the  fact  that  the  meta- 
phosphates  of  the  earthy  and  alkali  metals  and 
aluminium  are  insoluble  in  absolute  alcohol.3 

The  test  is  applied  as  follows:  Five  to  ten  cubic 
centimeters  of  the  oil  to  be  tested  are  dissolved  in 
about  five  cubic  centimeters  of  86°  gasolene  or 
ether,  and  about  fifteen  drops  of  the  phosphoric 

1  J.  Soc.  Chem.  Ind.,  16,  322  (1897). 

2  In  a  case  which  came  to  the  writer's  notice  the  oil  would  not 
flow  out  of  the  Saybolt  "A"  apparatus  at  70°,  at  85°  required 
1167",  and  at  110°,  181". 

3  Schweitzer  and  Lungwitz,  J.  Soc.  Chem.  Ind.,  13,  1178  (1894). 


PETROLEUM  PRODUCTS.  43 

acid  solution  (Appendix,  Reagents)  added,  shaken 
and  allowed  to  stand;  the  formation  of  a  flocculent 
precipitate  indicates  the  presence  of  soap.  An 
idea  of  the  kind  of  soap  can  be  often  gained  by 
adding  an  alcoholic  solution  of  PtCl4.  If  the  pre- 
cipitate becomes  crystalline  it  is  a  potash  soap; 
if  it  dissolves,  soda,  lime,  or  magnesia;  if  unchanged, 
alumina  or  iron. 

For  the  accurate  determination  of  these  com- 
pounds a  known  weight  of  the  oil  must  be  ignited, 
the  residue  determined  and  quantitatively  examined. 

Caoutchouc. — Holde1  states  that  one  to  two  per 
cent,  of  unvulcanized  caoutchouc  is  sometimes 
added  to  oils  to  increase  their  viscosity.  This  may 
be  detected  by  adding  three  parts  of  alcohol  to 
four  parts  of  the  ethereal  solution,  whereby  the 
rubber  material  is  precipitated  and  may  be  dried 
and  weighed. 

Tests  for  Antif luorescents.2 — It  is  often  desired  to 
remove  the  fluorescence  or  " bloom"  from  petroleum 
oils.  This  may  be  effected  by  refining  with  chromic 
acid,  or  more  easily  by  the  addition  of  a  small 
quantity  of  nitro-naphthalene  or  nitro-benzene. 
The  latter  may  often  be  detected  by  the  odor. 

The  test  is  made  by  boiling  about  one  cubic 
centimeter  of  the  oil  with  three  cubic  centimeters  of 
ten  per  cent,  alcoholic  potash  for  one  to  two  min- 
utes. If  either  of  the  nitro  compounds  be  present, 
a  blood-  or  violet-red  coloration  is  produced:  a 

1  "  Untersuchung  d.  SchmierSle,"  p.  183. 

2  Holde,  J.  Soc.  Chem.  Ind.,  13,  906  (1893). 


44  PHYSICAL  AND  CHEMICAL  TESTS. 

pure  mineral  oil  is  changed  only  to  yellow  or  brown- 
ish-yellow by  this  treatment.  In  case  the  char- 
acteristic color  does  not  appear  the  following  test 
may  be  applied.1  It  depends  upon  the  reduction 
of  the  nitro  bodies  to  their  amines. 

A  few  cubic  centimeters  of  the  oil  are  heated 
with  feathered  tin  and  hydrochloric  acid  in  an 
Erlenmeyer  flask  for  ten  minutes:  this  can  be 
aided  by  the  introduction  of  a  piece  of  platinum 
wire.  The  oil  is  separated  by  a  separatory  funnel 
and  filtration  through  a  wet  filter,  the  filtrate 
treated  in  another  separatory  with  sodium  hydrate 
until  the  tin  hydrate  redissolves  and  shaken  out 
with  10-20  cc.  of  ether.  The  amines  go  into 
solution  in  the  ether,  giving  to  it  a  violet  color 
and  fluorescence  in  the  case  of  a-napthylamine. 
These  can  be  recognized  by  their  odor,  that  of 
napthylamine  being  very  characteristic.  The  latter 
may  be  recognized  by  dissolving  in  hydrochloric 
acid,  evaporating  the  latter,  and  upon  treatment 
with  ferric  chloride  obtaining  an  azure-blue  precipi- 
tate. This  changes  when  filtered  off  to  purple-red 
and  the  filtrate  to  violet. 

Aniline  can  be  recognized  by  solution  in  con- 
centrated sulphuric  acid  and  the  red  and  then 
blue  color  which  appears  on  the  addition  of  a  small 
crystal  of  potassium  bichromate.  Free  aniline  is 
also  temporarily  colored  violet  by  a  solution  of 
bleaching  powder. 

1  Holde,  "Untersuchung,  u.  s.  w."  p.  186. 


PETROLEUM  PRODUCTS.  45 

To  ascertain  if  an  oil  be  fluorescent,  place  a  few 
drops  upon  a  piece  of  hard  rubber  or  other  black 
surface  and  observe  if  any  trace  of  blue  color  be 
perceptible. 

Test  for  Fatty  Oils. — To  detect  small  quantities 
of  fatty  oil  (one-quarter  to  two  per  cent.)  Lux1 
recommends  heating  a  few  cubic  centimeters  of  the 
oil  for  fifteen  minutes  with  some  bits  of  sodium  in 
a  test-tube  in  an  oil-bath;  a  similar  test  is  made 
with  sodium  hydrate.  The  temperature  employed 
should  be  for  light  oils  about  230°,  for  dark  oils 
2500.2  In  case  fatty  oil  be  present,  the  contents  of 
one  or  both  of  the  tubes  solidify  to  a  jelly  of  greater 
or  less  consistence  according  to  the  amount  of  fatty 
oil  present. 

The  quantitative  determination  of  these  oils, 
as  for  example  in  cylinder  oils,  is  effected  after 
the  manner  of  determining  the  saponification  value 
(p.  65)  or  the  detection  of  unsaponifiable  oils  in 
fatty  oils  (p.  68). 

Schreiber3  adopts  a  similar  method  to  Sweetham 
and  Henriques,  in  that  he  dissolves  5  grams  of  the 
oil  in  25  cc.  of  benzole,  adds  25-50  cc.  §  alcoholic 
potash,  and  boils  for  half  an  hour  on  the  water- 
bath,  using  a  three-foot  glass  tube  as  a  condenser. 

Gumming  Test.4  —  This  is  designed  to  give  an 
idea  of  the  amount  of  change  that  may  be  expected 

1  Z.  anal.  Chem.,  24,  357  (1885). 

2  Holde,  Untersuchung  d.  Schmierole  u.  Fette,  p.  175. 

3  J.  Am.  Chem.  Soc.,  29,  74  (1907). 

4  Gill,  J.  Am.  Chem.  Soc.,  24,  467  (1902). 


46  PHYSICAL  AND  CHEMICAL  TESTS. 

in  a  mineral  oil  when  in  use.  These  resinified 
products  increase  the  friction  of  the  revolving  or 
rubbing  surfaces.1  It  is  also  a  measure  of  the 
amount  that  an  oil  will  " carbonize"  in  a  gas  or 
gasolene  engine  cylinder.  It  is  applied  after  the 
manner  of  the  Elaidin  Test,  by  thoroughly  mixing 
together  five  grams  of  the  oil  in  a  cordial  glass 
with  eleven  grams  of  nitrosulphuric  acid  and  cool- 
ing by  immersion  in  a  pan  of  water  at  10°-15°. 
Brownish  spots  or,  in  case  of  a  bad  oil,  masses, 
form  around  the  edges  and  become  red  in  the 
course  of  two  hours.  The  cordial  glass  is  filled 
successively  three  times  with  70°-86°  naphtha  and 
the  oil  dissolved  off  the  surface  of  the  acid,  the 
gasolene  solution  being  sucked  off  into  a  bottle 
with  an  air-pump.  Care  is  taken  not  to  suck  off 
any  of  the  tarry  matter  formed.  The  acid  can  be 
neutralized  with  ammonia  and  the  tar  can  be 
collected  on  a  tared  filter,  washed  with  gasolene 
that  leaves  no  residue  on  evaporation,  dried  at  a 
low  temperature,  and  weighed  as  gummy  matter. 
As  shown  by  long  practical  experience,  the  oil 
showing  the  least  tar  or  gum  is  the  best  oil;  it 
also  absorbs  the  least  oxygen. 

Friction  Tests. — The  writer  is  inclined  to  doubt 
if  friction  tests  are  worth  the  outlay  for  a  machine 
and  the  time  expended  in  their  execution.  With- 
out question  they  do  determine  the  relative  efficiency 
as  regards  lubricating  power  of  different  oils,  but 

1  Aisinman,  J.  Soc.  Chem.  Ind.,  14,  282  (1895). 


PETROLEUM  PRODUCTS.  47 

the  conditions  under  which  the  test  is  made  seldom 
occur  in  practice;  the  bearings  upon  which  the  oil 
is  tested  are  as  nearly  perfect  as  can  be  made,  and 
the  feed  and  load  are  as  regular  as  is  possible;  in 
other  words,  the  conditions  are  ideal. 

The  lubricating  power  of  an  oil  is  so  closely 
related  to  its  viscosity1  that  the  author  believes 
that  results  of  more  practical  value  can  be  obtained 
by  the  determination  of  the  viscosity  of  the  oils, 
and  subsequent  observation  of  their  behavior  in 
actual  use,  than  by  the  longer  and  more  trouble- 
some friction  test. 

In  case,  however,  it  be  desired  to  make  the 
friction  test,  the  following  machines,  it  is  believed, 
will  be  found  to  be  most  satisfactory  for  the  purpose. 

For  spindle  oils  and  light  lubricating  oils,  the 
Ordway-Woodbury  machine,2  described  in  the 
"Proceedings  of  the  American  Society  of  Mechan- 
ical Engineers/'  1880,  74,  and  1884,  136;  also  in 
Brannt,  " Petroleum  and  its  Products,"  p.  480. 

For  heavy  oils  and  railroad  work,  the  large 
machine  of  Thurston,2  described  in  his  "Friction 
and  Lost  Work  in  Machinery  and  Millwork, "  p. 
254;  also  in  Brannt,  p.  486;  also  in  Archbutt  and 
Deeley.3  Or  use  may  be  made  of  the  Richie*  machine 
made  by  the  Riehle  Bros,  of  Philadelphia.4 


1  Brannt,  "  Petroleum  and  its  Products,"  p.  510;    Woodbury, 
vide  infra. 

2  Made  by  the  Pratt  &  Whitney  Co.,  Hartford,  Conn. 

3  "Lubrication  and  Lubricants,"  1907,  pp.  332-348. 

4  Ibid.,  p.  359. 


48  PHYSICAL  AND  CHEMICAL  TESTS. 

For  machines  using  a  flooded  bearing  the  Beau- 
champ-Tower  machine,  described  in  the  "Proceed- 
ings of  the  Institution  of  Mechanical  Engineers  of 
Great  Britain/'  1883,  632;  1884,  29;  1885,  58; 
1888,  173;  1891,  131;  also  in  Archbutt  and  Deeley.1 

1  Ibid.,  p.  355. 


CHAPTER  III. 
ANIMAL  AND  VEGETABLE    OILS. 

THE  tests  most  commonly  employed  for  the 
identification  of  these  oils  are  as  follows:  specific 
gravity,  Valenta  test,  elaidin  test,  Maumene  test, 
heat  of  bromination  test,  iodine  number,  and 
saponification  value. 

In  addition  certain  special  and  commercial  tests 
are  applied,  as  Bechi  test,  Baudouin  test,  free  acid, 
spontaneous  combustion,  and  drying  test. 

Specific  Gravity. — This  is  usually  determined 
either  by  the  Westphal  balance  (page  36)  or  by  the 
picnometer. 

A  two-necked  flask  of  fifty  cubic  centimeters' 
capacity,  having  a  thermometer  carefully  ground 
into  one  neck,  the  second  one  being  a  narrow  tube 
bearing  the  mark,  is  most  suitable.  This  is  filled 
with  the  oil  to  be  examined,  cooled  to  15.5°  C.,1 
the  excess  of  oil  removed  and  weighed.  If  the 
weighings  be  made  to  0.5  milligram  and  a  correction 
applied  for  the  expansion  of  the  glass  by  the  differ- 
ence in  temperature,  =15.5°  — 4°  =  11. 5°  =—0.025 
per  cent,  of  the  value  obtained,  the  determination 
is  accurate  to  0.00002.2 

1  Allen  (Organic  Analysis,  33)  states  that  a  correction  of  0.00064 
can  be  made  for  each  variation  of  1°  C. 

2  Wright,  J.  Soc.  Chem.  Ind.,  11,  300  (1892). 

4  49 


50  PHYSICAL  AND  CHEMICAL  TESTS. 

For  the  determination  of  the  specific  gravity  of 
small  quantities  of  oil,  the  arseopicnometer  of  Eich- 
horn1  may  be  used.  Still  more  satisfactory  results 
can  be  obtained  by  weighing  one  or  five  cubic  centi- 
meters of  the  oil  carefully  measured  from  an  accu- 
rately calibrated  pipette.  Or  a  mixture  of  alcohol 
and  water  can  be  made  until  a  drop  of  oil  will  stay  in 
any  position  in  it,  and  its  specific  gravity  determined. 

Valenta  Test.2  —  Although  considered  by  some 
to  be  unreliable,  yet  as  the  indication  given  by  this 
test  may  be  of  value,  it  is  barely  worth  the  trouble 
of  execution.  It  depends  upon  the  solubility  of 
the  oil  in  glacial  acetic  acid. 

Enough  oil  is  poured  into  a  test-tube  to  fill  it 
to  the  depth  of  about  one  inch,  the  exact  height 
being  marked  by  the  thumb;  an  equal  quantity  of 
glacial  acetic  acid  is  poured  in,  that  is,  until  the 
acid  reaches  the  point  indicated  by  the  thumb. 
A  light  thermometer  is  placed  in  the  tube,  and  it  is 
heated  until  the  oil  dissolves, — shown  by  the  liquid 
becoming  homogeneous.  The  tube  is  now  allowed 
to  cool,  and  the  point  noted  at  which  it  begins  to 
become  thoroughly  turbid. 

Castor  oil  is  soluble  at  ordinary  temperatures, 
while  rape-seed  and  other  cruciferous  oils  are 
usually  insoluble  even  at  the  boiling  point  of  the 
acid.  The  temperatures  at  which  other  oils  become 
turbid  are  given  in  Table  VIII. 

1 Z.  anal.  Chem.,  30,  216  (1891). 

3  Valenta,  Dingier  polyt.  J.,  253,  418 ;  also  J.  Soc.  Chem.  Ind., 
3,  643  (1884). 


ANIMAL  AND  VEGETABLE  OILS.  51 

Elaidin  Test. — Although  this  is  not  a  quantita- 
tive test,  yet  its  ease  of  application  and  the  con- 
clusions which  may  be  drawn  from  it  render  it 
valuable.  It  depends  upon  the  change  of  the  liquid 
olein  into  its  solid  isomer  elaidin,  and  is  especially 
applicable  to  olive  and  lard  oils. 

Manipulation. — Five  grams  of  the  oil  are  weighed1 
— within  two  drops — into  a  cordial  glass,  seven 
grams  of  nitric  acid,  specific  gravity  1.34,  are  then 
weighed  into  it,1  and  two  pieces  of  copper  wire 
(0.6  to  1.0  gram)  added.  Place  the  glass  in  a  pan 
of  cold  water  at  about  12°  C.,  and  stir  with  a 
short  glass  rod  about  twenty  to  thirty  turns,  not 
only  with  a  rotary  movement  but  also  with  an 
up-and-down  motion,  so  as  to  mix  the  oil  and  the 
evolved  gas  thoroughly.  When  the  wire  has  dis- 
solved, add  a  second  piece  and  stir  as  before.  This 
second  addition  should  furnish  gas  enough  if  the 
liquid  has  been  kept  cool  and  the  stirring  has  been 
thorough. 

At  the  end  of  the  first  hour  pure  lard  oil  will 
usually  show  flakes  of  a  wax-like  appearance,  and 
upon  standing  without  disturbance  and  at  the  same 
temperature  for  another  hour,  the  oil  will  have 
changed  to  a  solid  white  cake  hard  enough  to  bear 
several  ounces'  weight  or  admit  of  lifting  the  glass 
and  contents  by  the  glass  rod. 

Most  of  the  fish  and  seed  oils  yield  a  pasty  or 
buttery  mass  separating  from  a  fluid  portion, 

1  Not  on  the  analytical  balance. 


52  PHYSICAL  AND  CHEMICAL  TESTS. 

whereas  olive,  almond,  peanut,  lard,  sperm,  and 
sometimes  neat's-foot  oil,  yield  a  solid  cake. 

Instead  of  using  nitric  acid  and  copper,  sulphuric 
acid  of  46°  Baume,  containing  a  little  nitric  acid 
and  saturated  at  0°  C.  with  nitric  oxide,  may  be 
employed. 

A  test  should  always  be  made  at  the  same  time  with 
an  oil  of  undoubted  purity. 

Notes. — If  the  oil  be  stirred  too  much  or  too 
frequently,  or  is  too  warm,  it  has  no  opportunity 
to  form  a  hard  cake. 

Hiibl  states  that  all  attempts  to  make  the  test  a 
quantitative  one  have  resulted  in  failure. 

Mercury  can  be  used  instead  of  copper. 

Cailletet's  method,1  in  which  a  smaller  quantity 
of  oil  is  used  and  sulphuric  and  nitric  acids  allowed 
to  act  upon  it  in  a  boiling  water-bath,  cannot,  in 
the  experience  of  the  writer,  be  depended  upon  to 
give  reliable  results. 

Maumene  Test. — While  this,  like  the  preceding, 
is  not  a  quantitative  test,  yet  the  indications 
afforded  by  it  are  of  more  value  in  many  cases  than 
those  obtained  by  quantitative  methods,  as,  for 
example,  the  saponification  value.  It  depends 
upon  the  heat  developed  by  the  mixing  of  the  oil 
with  strong  sulphuric  acid.  This  takes  place  in 
a  small  beaker  seven  and  one  half  to  nine  centi- 
meters deep  and  of  one  hundred  and  fifty  cubic 
centimeters'  capacity,  packed  in  an  agate-ware 
cup  with  dry  felt  or  cotton  waste  packing. 

1  Milliau,  J.  Am.  Chem.  Soc.,  15,  156  (1893). 


ANIMAL  AND  VEGETABLE  OILS.  53 

Manipulation. — Fifty  grams  of  the  oil  are  weighed 1 
into  the  beaker  to  within  two  drops,  and  its  tem- 
perature noted  by  a  thermometer.  Ten  cubic 
centimeters  of  sulphuric  acid  are  now  run  gradu- 
ally into  the  oil, — allowing  the  graduate  to  drain 
five  seconds, — the  mixture  being  stirred  at  the 
same  time,  and  the  stirring  continued  until  no 
further  increase  in  temperature  is  noted.  The 
highest  point  at  which  the  thermometer  remains 
constant  for  any  appreciable  time  is  observed,  and 
the  difference  between  this  and  the  initial  tempera- 
ture is  the  "rise  of  temperature."  This  varies 
with  the  strength  of  the  acid  employed,  and  to 
secure  uniformity2  the  results  should  be  expressed 
by  dividing  the  rise  of  temperature  with  the  oil  by 
the  rise  of  temperature  with  water,  and  multiply- 
ing by  one  hundred.  This  is  called  the  "specific 
temperature  reaction."  The  rise  of  temperature 
with  water  is  determined  in  the  same  manner  as 
with  oil,  using  the  same  vessel. 

Notes. — In  performing  this  test  it  is  important 
that  the  oil  and  acid  be  of  the  same  temperature, 
attained  by  keeping  them  beside  each  other. 

The  strength  of  acid  should  be  as  far  as  possible 
the  same;  it  should  be  determined  not  by  specific 
gravity,  but  by  titration,  as  one  hundred  per  cent, 
and  ninety-four  and  three-tenths  per  cent,  acid 
have  the  same  specific  gravity. 

1  Not  on  the  analytical  balance. 

2  Tortelli,  J.  Soc.  Chem.  Ind.,  23,  668  (1904),  is  unable  to  secure 
uniformity  in  this  way. 


54  PHYSICAL  AND  CHEMICAL  TESTS. 

For  concordant  results  the  conditions  should  be 
the  same,  and  the  same  apparatus  should  be  used. 
In  case  the  test  is  to  be  applied  to  a  drying  oil,  it 
should  be  diluted  one-half  with  a  mineral  oil, 
25°  paraffine,  for  example,  thoroughly  mixing  them. 
The  "rise  of  temperature"  is  then,  the  rise  of  tem- 
perature of  mixture  minus  half  the  rise  of  tempera- 
ture of  fifty  grams  of  mineral  oil,  multiplied  by  two. 

It  is  advisable  to  make  a  test  at  the  same  time  with 
an  oil  of  known  purity.  Results  should  agree  within 
two  per  cent.  By  the  use  of  the  Hubl  formula,  p.  62, 
substituting  thermal  values,  results  comparable  with 
those  obtained  with  the  iodine  value  can  be  obtained. 

Sherman,  Danziger,  and  Kohnstamm1  have 
studied  this  method  with  the  idea  of  eliminating 
the  errors.  Rather  than  dilute  the  oil  with  a  min- 
eral oil  they  dilute  the  acid,  using  one  of  eighty- 
nine  per  cent.  The  results  obtained  are  a  little 
lower  for  vegetable  oils  and  a  little  higher  for  ani- 
mal oils  than  those  usually  found  with  the  strong 
acid  as  employed  by  Thomson  and  Ballantyne- 
Mitchell2  uses  an  inert  diluent — carbon  tetrachlo- 
ride — in  a  vacuum-jacketed  tube  and  one-fifth  the 
quantities;  all  oils  are  diluted.  He  finds  that  the 
results  obtained  are  in  close  agreement  with  the 
bromine  thermal  values;  further,  that  the  test  may 
be  of  use  in  determining  the  degree  of  oxidation 
of  fats  and  oils,  the  figures  becoming  greater  with 
the  age  of  the  oil. 

1  J.  Am.  Chem.  Soc.,  24,  266  (1902). 
1  Analyst,  26,  169  (1901). 


ANIMAL  AND  VEGETABLE  OILS.  55 

Data  upon  various  oils  will  be  found  in  Table 
VIII. 

REFERENCES. 

MAUMENE,  Compt.-Rend.,  35,  572  (1852). 
ELLIS,  J.  Soc.  Chem.  Ind.,  5,  361  (1886). 

THOMSON  and  BALLANTYNE,  J.  Soc.  Chem.  Ind.,  10,  234  (1891). 
RICHMOND,  Analyst,  20,  58  (1895). 
MUNROE,  Am.  Pub.  Health  Ass'n,  10,  236  (1884). 

Heat  of  Bromination  Test.  —  This  test,  which 
was  proposed  by  Hehner  and  Mitchell,1  consists  in 
observing  the  rise  of  temperature  when  bromine  is 
added  to  a  solution  of  the  oil  in  chloroform.  It 
occupies  a  middle  position  between  the  Maumene, 
being  more  accurate  than  it,  and  the  Hiibl,  than 
which  it  is  less  delicate;  by  multiplying  by  a  factor, 
different  for  each  instrument,  the  results  obtained 
can  be  expressed  in  figures,  which  are  a  close  ap- 
proximation to  those  obtained  by  the  Hiibl  method. 

The  process  has  not  found  extensive  application, 
and  for  a  description  of  the  method  of  execution 
reference  may  be  had  to  articles  by  Wiley,  J.  Am. 
Chem.  Soc.,  18,  378  (1896),  and  Gill  and  Hatch, 
id.,  21,  27  (1899). 

Iodine  Number  or  Value.  —  This  is  the  percent- 
age of  iodine  absorbed  by  an  oil;  the  method  de- 
pends upon  the  fact  that  different  oils  absorb 
different  amounts  of  the  halogens;  the  process  is 
mainly  one  of  addition,  although  small  quantities 
of  substitution  products  are  formed.  For  example, 
the  unsaturated  body  olein,  (C17H33COO)3C3H5, 

1  Analyst,  20,  146  (1895). 


56  PHYSICAL  AND  CHEMICAL  TESTS. 

when  brought  in  contact  with  iodine  takes  up  six 
atoms  and  forms  the  addition  product,  di-iodo 
stearin,  (C17H33I2COO)3C3H5.  Palmitin,  (C15H31- 
COO)3C3H5,  when  similarly  treated,  forms  no  addi- 
tion product,  but  a  small  quantity  of  the  substitu- 
tion product,  iodo-palmitin,  (C15H30ICOO)3C3H5,  and 
the  hydrogen  displaced  unites  with  the  iodine  to  form 
hydriodic  acid.  The  quantity  of  hydriodic  acid  thus 
formed  is  a  measure  of  the  amount  of  substitution.1 

1.  HANUS'S  METHOD. — Manipulation. — From  0.12 
to  0.15  gram  of  a  drying  oil,  0.2  to  0.3  gram  of  a 
non-drying  oil,  or  0.6  to  0.7  gram  of  a  solid  fat,  is 
accurately  weighed  into  a  dry  two  hundred  cubic 
centimeter  bottle.  This  should  be  of  colorless  glass 
and  be  provided  with  a  well-ground  stopper.  This  is 
best  effected  by  pouring  out  about  five  grams  of  the 
oil  into  a  No.  1  beaker  containing  a  short  stirring 
rod,  and  setting  it  into  a  watch-glass  upon  the  pan 
of  the  analytical  balance.  The  whole  system  is 
weighed,  the  beaker  removed,  and  several  drops  of 
oil  transferred  to  the  bottle  by  dropping  down 
the  rod,  being  careful  that  no  oil  touches  the  neck. 
Eight  drops  are  approximately  0.2  gram.  The 
beaker  is  replaced  in  the  watch-glass  and  the 
system  again  weighed,  the  difference  in  weight 
being  the  amount  of  oil  in  the  bottle. 

The  oil  is  dissolved  in  10  cc.  of  chloroform,  30 
cc.  of  the  iodine  solution  (Appendix,  " Reagents") 
added,  —  best  from  a  burette,  —  and  allowed  to 

1  McDhiney,  J.  Am.  Chem.  Soc.,  16,  275  (1894). 


ANIMAL  AND  VEGETABLE  OILS.  57 

stand  with  occasional  shaking  for  fifteen  minutes; 
with  oils  of  an  iodine  number  of  less  than  100, 
ten  minutes  suffices;  15  cc.  of  potassium  iodide 
solution1  are  added  and  the  solution  titrated,  with 
or  without  the  addition  of  starch,  with  sodium 
thiosulphate  until  the  halogen  disappears. 

At  the  same  time  at  which  the  oil  was  prepared 
two  " blanks"  should  be  prepared  similarly  in 
every  way  to  the  actual  tests,  except  in  the  addi- 
tion of  the  oil,  and  treated  in  every  respect  like 
them;  the  strength  of  the  thiosulphate  solution 
should  also  be  determined  the  same  day  on  which 
this  test  is  carried  out. 

Standardization  of  the  Thiosulphate  Solution. — 
Ten  cubic  centimeters  of  potassium  iodide  and  one 
hundred  cubic  centimeters  of  water  are  poured 
into  the  Erlenmeyer  flask;  twenty  cubic  centi- 
meters of  the  bichromate  solution,  equivalent  to 
0.2  gram  of  iodine,  are  now  measured  in  with  a 
pipette,  and  to  this  five  cubic  centimeters  of  strong 
hydrochloric  acid  added  and  the  mixture  shaken 
for  three  minutes.  It  is  now  titrated  with  the 
thiosulphate  solution  until  the  yellow  color  of  the 
iodine  has  almost  disappeared;  starch  paste  is  now 
added,  and  the  titration  continued  until  the  deep- 
blue  color  of  the  solution  changes  to  a  sea-green, — 
due  to  CrCl3,  —  which  is  usually  brought  about 
by  the  addition  of  a  single  drop. 

The  reactions  involved  are: 

1  This  is  the  original  method.  Tolman  adds  here  100  cc.  water 
as  in  the  Hiibl  method. 


58  PHYSICAL  AND  CHEMICAL  TESTS. 

KAA + 14HC1 = 2CrCl3 + 2KC1  +  7H8O + 30,; 

3C12  +  6KI  =  6KC1  +  3I2; 
6Na2S2O3 + 3I2 = 3Na2S4Oc + 6NaI. 

Notes. — Wijs1  uses  iodine  chloride  instead  of 
bromide;  it  is  more  troublesome  to  prepare  and 
gives  results  about  1.2  points  higher.2  Either  of 
these  methods  has  the  advantage  over  HiibPs, — 
first,  that  the  solutions  keep  better,  remaining  prac- 
tically unchanged  for  several  months;  secondly^ 
that  the  action  is  about  sixteen  times  as  rapid,  it 
being  completed  in  fifteen  minutes;  thirdly,  that 
the  solutions  are  cheaper. 

Acetic  acid  cannot  be  displaced  by  carbon  tetra- 
chloride  as  a  solvent,  as  the  last  traces  of  iodine  are 
difficult  to  remove  from  it.  The  acetic  acid  used 
should  be  at  least  99.5  per  cent,  and  show  no  reduc- 
tion with  potassium  bichromate  and  sulphuric  acid. 

2.  HUBL'S  METHOD. — Manipulation. — The  oil  is 
weighed  out  as  in  1,  into  three  hundred  cubic 
centimeter  bottles,  except  that  about  twenty-five 
per  cent,  more  may  be  used. 

The  oil  is  now  dissolved  in  ten  cubic  centimeters 
of  chloroform,  thirty  cubic  centimeters  of  iodine 
and  mercuric  chloride  solution  added,  the  bottle 
placed  in  a  dark  closet,  and  allowed  to  stand,  with 
occasional  gentle  shaking,  for  four  hours.  If  the 
solution  becomes  nearly  decolorized  after  two 
hours,  an  additional  quantity  should  be  added. 

^erichte,  31,752  (1898). 

2  Tolman  and  Munson,  J.  Am.  Chem.  Soc.,  25,  244  (1903).  See 
Appendix,  Table  XIII. 


ANIMAL  AND  VEGETABLE  OILS.  59 

One  hundred  cubic  centimeters  of  distilled  water 
and  twenty  cubic  centimeters  of  potassium  iodide 
are  added  to  the  contents,  and  the  excess  of  iodine 
titrated  with  sodium  thiosulphate.  If  at  this  point 
a  red  precipitate  (HgI2)  is  formed,  more  potassium 
iodide  should  be  added.  As  the  chloroform  dis- 
solves some  of  the  iodine,  the  titration  can  proceed 
until  the  chloroform  layer  is  nearly  colorless,  then 
the  starch  solution  is  added,  and  the  operation  con- 
tinued to  the  disappearance  of  the  blue  color. 

"Blanks"  should  be  titrated  as  with  the  fore- 
going process,  page  57. 

Notes. — The  method  was  proposed  by  Cailletet  in 
1857,  made  use  of  by  Mills  and  Snodgrass1  in  1883, 
using,  however,  bromine  and  carbon  bisulphide, 
and  described  in  almost  its  present  form  by  Hiibl.2 
The  chief  factors  in  its  execution  are  (1)  strength 
of  the  iodine  solution;  (2)  the  quantity  used; 
and  (3)  the  length  of  its  time  of  action. 

I.  The  Strength  of  Iodine  Solution. — According 
to  HiibPs  original  memoir,  the  solutions  can  be 
kept  indefinitely  when  mixed. 

Fahrion3  states  that  the  solution  deteriorated  as 
much  as  from  seventeen  to  twenty-three  per  cent, 
in  eight  days.  Ballantyne4  confirms  the  deteriora- 
tion, but  finds  it  much  less,  five  to  eight  per  cent. 


1 J.  Soc.  Chem.  Ind.,  2,  435  (1883). 

'Dingier  polyt.  J.,  253,  281;    also  J.  Soc.  Chem.  Ind.,  3,  641 
(1884). 

3  J.  Soc.  Chem.  Ind.,  11,  183,  abstr.  (1892). 
•Id.,  13,  1100,  abstr.  (1894). 


60  PHYSICAL  AND  CHEMICAL  TESTS. 

in  thirty-eight  days.  This  weakening  of  the  solu- 
tion is  probably  due  to  the  hydriodic  acid  formed 
by  the  action  of  the  iodine  upon  the  alcohol.1 

The  mercuric  chloride  acts  apparently  as  a  carrier 
of  iodine,  as  the  reaction  takes  place  very  slowly 
without  it.  (Gantter.)2  Waller3  finds  that  the 
addition  of  fifty  cubic  centimeters  HC1,  specific 
gravity  1.19,  to  the  mixed  iodine  solution  preserves 
it  for  months.  Of  the  other  metallic  chlorides, 
CoCl2  gives  the  highest  true  iodine  value,  MnCl2, 
MnBr2,  and  NiCl2  cause  practically  no  addition. 
(Schweitzer  and  Lungwitz.)4 

2.  The  Quantity  of  Iodine  Solution  used.  —  The 
mixed  iodine  solution  as  made  up  should  require 
about  fifty-three  cubic  centimeters  of  the  thiosul- 
phate.  Before  using,  a  rough  titration  should  be 
made,  and  if  it  be  much  weaker  than  this,  a  pro- 
portionately larger  amount  added.  The  action  of 
a  large  excess  of  iodine  is  to  increase  the  substitu- 
tion rather  than  addition;  increase  in  temperature 
or  in  time  produces  the  same  effect.5 

The  excess  of  iodine  recommended  is  from  one 
hundred  and  fifty  to  two  hundred  and  fifty  per 
cent.;  some  observers  recommend  from  four  hun- 
dred6 to  six  hundred  per  cent.7 


1  J.  Soc.  Chem.  Ind.,  14,  130  (1895). 

2  Id.,  12,  717,  abstr.  (1893). 
'Chem.  Ztg.,  19,  1786,  1831  (1895). 

4  J.  Soc.  Chem.  Ind.,  14,  1031  (1895). 

6  J.  Soc.  Chem.  Ind.,  12,  717,  abstr.  (1893). 
•Id.,  14,  1031  (1895). 

7  Holde,  Mitt.  kgl.  Techn.  Versuchs.,  9,  81  (1891). 


ANIMAL  AND  VEGETABLE  OILS.  61 

3.  Length  of  Time. — Two  hours  is  sufficient  for 
olive  oil,  tallow,  and  lard,  while  for  linseed  oil, 
balsams,  and  resins  twenty-four  hours  should  be 
allowed.1 

Waller2  thinks  that  the  " iodine  number"  is  really 
the  sum  of  changes  in  the  fat  due  to  absorption  of 
iodine,  oxygen,  and  chlorine. 

The  two  latter  come  from  the  interaction  of  the 
iodine,  and  mercuric  chloride  setting  free  chlorine, 
which  sets  free  some  oxygen  from  the  water. 

Schweitzer  and  Lungwitz3  obtain  what  they 
term  "the  true  iodine  value"  by  acting  upon  the 
oils  for  twenty-five  minutes  at  45°  C.  with  iodine 
dissolved  in  carbon  bisulphide  and  in  the  presence 
of  a  considerable  quantity  of  mercuric  chloride. 
Practically  no  hydriodic  acid  is  formed  under  these 
conditions,  and  yet  in  the  case  of  oleic  acid  it  ab- 
sorbs more  than  the  theory  requires. 

They  have  studied  further  the  effect  of  various  sol- 
vents for  iodine  instead  of  ethyl  alcohol,  as  methyl 
alcohol,  ether,  carbon  tetrachloride  and  bisulphide. 

Ingle4  has  shown  that  the  free  acid  formed  during 
the  process  is  due  to  the  action  of  water  upon  the 
iodochlorides.  Some  of  these  are  reduced  by  potas- 
sium iodide  with  liberation  of  iodine  and  conse- 
quent reduction  in  the  iodine  absorption.  Iodine 
chloride  is  the  active  agent,  and  not  hypoiodous  acid. 


1  Dieterich,  J.  Soc.  Chein.  Ind.,  12,  381  (1893). 

2  Analyst,  20,  280,  (1895). 

3  J.  Soc.  Chem.  Ind.,  14,  1031  (1895). 
•  J.  Soc.  Chem.  Ind.,  21.  587  (1902). 


62  PHYSICAL  AND  CHEMICAL  TESTS. 

Gill  and  Adams,1  using  a  solution  of  iodine  and 
mercuric  iodide  in  absolute  methyl  alcohol,  have 
diminished  the  amount  of  substitution  that  takes 
place.  Oleic  acid  added  the  theoretical  amount  of 
iodine,  and  even  stearic  acid  about  seven  per  cent. 

For  the  calculation  of  the  percentage  of  adulter- 
ation of  one  oil  by  another,  Hiibl  gives  the  follow- 
ing formula:2 

"Let  x  =  percentage  of  one  oil  and  y  =  percent- 
age of  the  other  oil,  further,  m  =  iodine  value  of 
pure  oil  x,  n  of  pure  oil  y,  and  7  of  the  sample 
under  examination,  then 

x_100  (7— n)  „ 
in — n 

He  further  states  that  the  age  of  the  oil,  provided 
it  be  not  rancid  or  thickened,  is  without  influence 
on  the  iodine  value.  Ballantyne3  finds  that  light 
and  air  diminish  the  iodine  number. 

As  might  be  expected,  the  iodine  value  is  inversely 
proportional  to  the  cold  test. 

The  method,  as  will  be  seen,  is  a  conventional  one, 
and  the  best  results  will  be  obtained  by  using  mea- 
sured quantities  of  reagents  and  carrying  through 
the  process  in  the  same  manner  every  time.4 

The  calculation  is  perhaps  most  easily  made  as 
follows:  Subtract  the  number  of  cubic  centimeters 


1 J.  Am.  Chem.  Soc.,  22,  13  (1900). 
'Dingier  polyt.  J.,  253,  281  (1884). 

3  J.  Soc.  Chem.  Ind.,  10,  31  (1891). 

4  If,  for  example,  the  water  be  added  before  the  iodide  solution, 
the  iodine  number  is  changed  by  0.3  per  cent. 


ANIMAL  AND  VEGETABLE  OILS.  63 

of  thiosulphate  used  for  the  titration  of  the  oil  from 
that  obtained  by  titrating  the  blank, — this  gives 
the  thiosulphate  equivalent  to  the  iodine  absorbed 
by  tjie  oil.  Multiply  this  number  (of  cubic  centi- 
meters) by  the  value  of  the  thiosulphate  in  terms 
of  iodine,  and  the  result  is  the  number  of  grams  of 
iodine  absorbed  by  the  oil;  this  divided  by  the 
weight  of  oil  used  and  multiplied  by  one  hundred 
gives  the  iodine  number. 

In  case  it  be  desired  to  recover  the  iodine  used, 
reference  may  be  had  to  an  article  by  Dieterich, 
abstracted  in  the  Jour.  Soc.  Chem.  Ind.,  15,  680 
(1896). 

Oxidized  Oils — Iodine  Number  of. — To  find  the 
original  iodine  number  of  a  semi-drying  or  non- 
drying  oil  which  has  been  altered  by  atmospheric 
oxidation,  add  0.8  to  the  iodine  number  found  on 
the  altered  sample  for  each  increase  of  0.001  in 

(15  5°  C  \  * 
taken  at      '  ] • 

lo.o    u./ 

Bromine  Number  or  Value. — The  iodine  method 
just  described  has,  among  others,  the  disadvantage 
that  it  fails  to  distinguish  between  addition  and 
substitution;  this  is  sometimes  of  importance,  and 
to  accomplish  it  Mcllhiney2  makes  use  of  the  bro- 
mine absorption. 

Manipulation. — From  0.2  to  0.3  gram  of  a  drying 
oil,  0.4  to  0.5  of  a  non-drying  oil,  or  1.0  to  1.2  grams 
of  a  solid  fat,  are  accurately  weighed  into  the 

Sherman  and  Falk.,  J.  Am.  Chem.  Soc.,  27,  608  (1895). 
» J.  Am.  Chem.  Soc.,  21,  1084  (1899). 


64  PHYSICAL  AND  CHEMICAL  TESTS. 

three  hundred  cubic  centimeter  bottle,  as  in  the 
iodine  number  (page  58). 

The  oil  is  dissolved  in  ten  cubic  centimeters  of 
carbon  tetrachloride,  and  twenty  cubic  centimeters 
of  bromine  solution  (Appendix,  Reagents)  added, 
best  from  a  burette.  After  allowing  it  to  stand  two 
minutes  by  the  watch,  twenty  or  thirty  cubic 
centimeters  of  potassium  iodide  are  added,  in  the 
manner  described  below,  the  amount  depending 
upon  the  excess  of  bromine.  To  prevent  loss  of 
bromine  and  hydrobromic  acid,  a  short  piece  of 
thin  and  wide  rubber  tubing — "bill  tie  tubing" — 
is  slipped  over  the  lip  of  the  bottle,  thus  forming 
a  well  around  the  stopper;  some  of  the  iodide 
solution  is  poured  into  this  and  the  bottle  cooled 
in  cracked  ice.  Upon  removing  the  stopper  the 
solution  is  sucked  into  the  bottle,  it  is  shaken  to 
insure  the  solution  of  the  vapors,  and  the  remainder 
of  the  reagent  added.  The  iodine  liberated  is 
titrated  by  sodium  thiosulphate  in  the  usual  way. 

When  this  titration  is  finished,  five  cubic  centi- 
meters of  the  potassium  iodate  solution  are  added 
and  the  titration  repeated.  The  iodine  liberated 
in  this  reaction  is  equivalent  to  the  hydrobromic 
acid  present.  Blank  determinations  should  be  made 
with  the  reagents  used,  as  with  the  iodine  number. 

Notes.  —  Oftentimes,  particularly  with  resins, 
emulsification  of  the  solution  takes  place,  masking 
the  end  point.  This  can  be  prevented  by  the  addi- 
tion of  fifty  or  a  hundred  cubic  centimeters  of  a 
ten  per  cent,  solution  of  salt. 


ANIMAL  AND  VEGETABLE  OILS.  65 

In  case  ice  be  not  at  hand,  the  vapors  will  prob- 
ably be  completely  absorbed  by  passing  through 
the  iodine  solution  in  the  rubber  well. 

The  reactions  involved,  in  addition  to  those  on 
pages  56  and  58,  are: 

Palmitin. 

(C15H31COO)3C3H5  +  3Br2  =  (C15H30BrCOO)3C3H5  +  3HBr. 
3HBr  +  SKI  =  3KBr  +  3HI. 
6HI  +  KIO3  =  3I2  +  3H2O  +  KI. 

The  calculation  is  similar  to  that  followed  in  the 
iodine  number  (page  62). 

The  percentage  of  bromine  found  as  hydrobromic 
acid  is  called  the  bromine  substitution  figure,  and  the 
total  percentage  absorbed,  less  twice  the  bromine 
substitution  figure,  gives  the  bromine  addition  figure. 

The  method  has  the  further  advantages  that  it 
is  rapid,  the  bromine  solution  is  permanent  and 
inexpensive.  For  data  upon  various  oils,  see 
Table  XII. 

Saponification  Value. — This  is  expressed  by  the 
number  of  milligrams  of  potassium  hydrate  necessary 
to  saponify  one  gram  of  the  oil.  It  is  called  from 
the  originator  "  Koettstorf er i  number  or  value, "  also 
"  Saponification  number, "  and  must  not  be  con- 
founded with  "  Saponification  equivalent"  as  proposed 
by  Allen,2  which  is  the  number  of  grams  of  oil 
saponified  by  56.1  grams  of  potassium  hydrate. 

Manipulation. — One  to  two  grams  of  the  oil  are 
weighed  out  into  a  two  hundred  cubic  centimeter 

1  Z.  anal.  Chem.,  18,  199  (1879). 

2  Commercial  Organic  Analysis,  2,  40. 


66  PHYSICAL  AND  CHEMICAL  TESTS. 

Erlenmeyer  flask  (as  in  the  iodine  value,  q.  v., 
page  56)  and  saponified  by  twenty-five  cubic 
centimeters  §  alcoholic  potash  accurately  measured 
from  a  burette,  by  heating  upon  a  water-bath,  a 
one-inch  funnel  being  inserted  in  the  flask. 

When  the  saponification  is  complete,  shown  by 
the  homogeneity  of  the  solution,  a  few  droops  of 
phenolphthalein  are  added  and  the  excess  of  alkali 
titrated  with  £  hydrochloric  acid.  Two  blank 
determinations  of  the  strength  of  the  §  potassium 
hydrate  must  be  made  simultaneously,  by  heating 
25  c.c.  under  the  same  conditions  as  when  mixed 
with  the  oil  and  for  the  same  length  of  time. 

Notes. — Many  prefer  to  cork  the  flasks  tightly 
and  tie  down  the  stoppers,  thus  saponifying  under 
pressure;  others  make  use  of  a  return  flow  con- 
denser, oftentimes  merely  a  long  glass  tube. 

Smetham1  adds  twenty  cubic  centimeters  of 
ether  and  finds  that  it  aids  saponification.  Hen- 
riques2  uses  three  to  four  grams  of  oil,  twenty-five 
cubic  centimeters  of  petroleum  ether,  and  twenty- 
five  cubic  centimeters  of  normal  alcoholic  potash, 
saponifying  in  the  cold  by  allowing  to  stand  over 
night;  the  advantage  consists  in  preventing  the 
change  in  the  solution  by  boiling. 

Mcllhiney3  has  applied  the  process  to  dark-col- 
ored substances  by  making  use  of  the  principle 

1  Analyst,  18,  193  (1893). 
ZZ.  angew.  Chemie,  721  (1895). 

3  J.  Am.  Chem.  Soc.,  1 6, 409  (1894).  For  a  discussion  of  the  theory 
of  the  process,  see  Lewkowitsch,  J.  Soc.  Chem.  Ind.,  17,  1107  (1898). 


ANIMAL  AND  VEGETABLE  OILS.  67 

that  when  ammonium  chloride  is  added  to  a  neutral 
soap  solution,  and  the  mixture  distilled,  the  amount 
of  ammonia  freed  is  equivalent  to  the  quantity 
of  alkali  combined  with  the  fatty  acids.  As  a 
description  of  the  process  is  beyond  the  scope  of 
the  present  volume,  reference  must  be  had  to  the 
original  article. 

As  ordinarily  prepared,  the  alcoholic  potash 
solution  turns  rapidly  reddish-brown,  so  that  it 
is  very  difficult  to  note  the  end  point.  This  trouble 
can  be  partially  avoided  by  adding  a  drop  or  two 
of  the  solution  to  the  diluted  indicator  contained 
upon  a  tile  after  the  manner  of  the  titration  of 
iron  by  bichromate.  As  the  color  is  probably  due 
to  the  polymerization  of  the  aldehyde  formed  by 
the  oxidation  of  the  alcohol,  it  is  more  satisfactory 
to  use  for  the  preparation  of  the  potash  solution 
an  alcohol  which  is  practically  aldehyde  free.  This 
is  best  made,  according  to  Dunlap,1  as  follows: 
one  and  one-half  grams  of  silver  nitrate  are  dis- 
solved in  3  cc.  water,  added  to  one  liter  of  alcohol 
and  thoroughly  shaken;  three  grams  of  potassium 
hydrate  are  dissolved  in  15  cc.  warm  alcohol  and, 
after  cooling,  added  to  the  alcoholic  silver  nitrate 
and  thoroughly  shaken  again,  best  in  a  tall  bottle 
or  cylinder.  The  silver  oxide  is  allowed  to  settle, 
the  clear  liquid  siphoned  off  and  distilled.  Alcoholic 
potash  made  up  from  this,  using  the  so-called 
"  potash  by  alcohol/'  will  give  a  solution  which 
will  remain  water-white  for  weeks. 

1 J.  Am  Chem.  Soc.,  28,  397  (1906). 


68  PHYSICAL  AND  CHEMICAL  TESTS. 

The  writer  has  found,  if  the  stock  solution  be 
kept  under  an  atmosphere  of  hydrogen,  that  the 
coloration  by  standing  is  almost  entirely  prevented. 

Detection  of  Unsaponifiable  Oils. — The  qualita- 
tive detection  takes  place  by  observing  the  be- 
havior of  the  solution  obtained  by  boiling  the  oil 
with  alcoholic  potash  when  diluted  with  warm 
water.  Any  unsaponifiable  material  will  manifest 
itself  as  oily  drops  in  the  clear  alcoholic  solution, 
or  as  a  whitish  cloud  on  the  addition  of  water. 

The  quantitative  determination  may  take  place 
in  two  ways:  1.  From  the  saponification  number. 
2.  By  gravimetric  methods. 

1.  From  the  Saponification   Number. — By  Table 
VIII  it   will    be   noticed    that,   except   for  Castor, 
Rape,  and  Sperm  oils,  the  saponification  number 
averages  193.     If  the  number  found  be  divided  by 
this  figure,  the  percentage  of  saponifiable  matter 
will  be  obtained;  this  subtracted  from  100  will  give 
the  unsaponifiable  matter.     This  method  gives  no 
idea  of  the  kind  of  saponifiable  matter. 

2.  By  Gravimetric    Methods.  —  The    procedure   is 
essentially  that  of  Spitz  and  Honig :  *    Ten  grams  of 
the  oil  are  boiled  fifteen  minutes  at  a  return-flow 
condenser  with  fifty  cubic  centimeters  of  five  per 
cent,  alcoholic  potash;2  forty  cubic  centimeters  of 
water  are   added   and  the   boiling  repeated.     The 
liquid  is  allowed  to  cool,  washed  into  a  separatory 

1  Z.  ang.  Chem.,  19,  565  (1891). 

2  The  potash  is  made  by  dissolving  purified  potash  in  the  smallest 
possible  quantity  of  water  and  adding  absolute  alcohol. 


ANIMAL  AND  VEGETABLE  OILS.  69 

funnel  with  fifty  per  cent,  alcohol  and  fifty  cubic 
centimeters  of  86°  gasolene,  thoroughly  shaken  and 
allowed  to  stand.  The  gasolene  layer  should  sepa- 
rate clearly  and  quickly  from  the  soap  solution  and 
the  latter  is  drawn  off;  the  gasolene  is  washed  two 
or  three  times  with  fifty  per  cent,  alcohol  to  extract 
any  soap,  and  these  washings  added  to  the  soap 
solution.  This  latter  is  extracted  until  upon  evap- 
oration the  gasolene  leaves  no  stain  upon  paper, 
care  being  taken  to  wash  the  gasolene  extracts  each 
time  with  fifty  per  cent,  alcohol;  three  extractions 
with  gasolene  are  usually  sufficient. 

The  gasolene  is  distilled  from  these  extracts,  the 
residue  heated  until  the  gasolene  odor  disappears, 
and  weighed.  From  the  appearance  of  the  residue 
some  idea  of  the  kind  of  unsaponifiable  matter 
can  be  obtained.  This  in  the  case  of  sperm  oil 
will  be  mainly  solid  alcohols,  probably  of  the 
ethylene  series. 

According  to  Schicht  and  Halpern1  this  method 
is  open  to  the  following  errors:  incomplete  saponi- 
fication,  incomplete  extraction,  solubility  of  soaps 
in  the  solvent,  and  the  solubility  of  the  unsaponi- 
fiable matter  in  the  washing  solution.  Their  im- 
proved method  is  as  follows:  five  grams  fat  with 
three  grams  solid  caustic  potash  dissolved  in  a  little 
water  and  25  cc.  absolute  alcohol  are  boiled  half 
an  hour  under  a  reflux  condenser.  After  cooling 
25  cc.  of  10  per  cent.  KC1  are  added  and  the  solu- 

1  Chem.  Ztg.,  31,  279  (1907). 


70  PHYSICAL  AND  CHEMICAL  TESTS. 

tion  is  then  shaken  four  times  with  200  cc.  petro- 
leum ether  distilling  under  60°.  The  petroleum 
ether  is  evaporated  and,  without  washing,  the 
residue  is  dissolved  in  25  cc.  absolute  alcohol  and 
the  solution  made  slightly  alkaline  with  normal 
alkali;  25  cc.  of  10  per  cent.  KC1  are  added  and 
the  shaking  with  petroleum  ether  repeated.  The 
petroleum  ether  solution  is  shaken  with  100  cc.  of 
50  per  cent,  alcohol  and  the  wash  solution  with 
100  cc.  petroleum  ether,  which  is  afterwards  washed 
with  100  cc.  of  50  per  cent,  alcohol.  After  combin- 
ing the  extracts  the  petroleum  ether  is  driven  off 
and  the  residue  dried  and  weighed. 

Notes. — Care  should  be  taken  to  use  gasolene 
which  leaves  no  residue  on  evaporation  at  100°  C. 

Identification  of  the  Unsaponifiable  Matter.— The 
unsaponifiable  matter  is  either  liquid  or  solid:  in 
case  it  is  liquid,  it  may  be  (1)  hydrocarbon  oils,  either 
mineral,  or  formed  by  the  distillation  of  waste 
fats,  as  wool  grease,  Chapter  VIII;  or  (2)  tar  oils, 
"dead  oils,"  etc.,  obtained  by  the  distillation  of 
coal  tar;  or  (3)  rosin  oils,  p.  118. 

If  it  be  a  question  of  one  of  these  three,  the  spe- 
cific gravity  will  usually  decide  it;  that  of  the 
hydrocarbon  oils  is  0.855  to  0.930,  of  the  rosin  oils 
0.96  to  0.99,  while  the  tar  oils  are  heavier  than 
water.  Rosin  oils  would  be  shown  by  the  Lieber- 
mann-Storch  test,  p.  120;  a  mixture  of  mineral  and 
tar  oils  would  be  identified  by  treatment  with  an 
equal  quantity  of  nitric  acid,  sp.  gr.  1.45,  both 
previously  cooled  to  15°  C.,  and  noting  the  rise 


ANIMAL  AND  VEGETABLE  OILS.  71 

of  temperature.  Mineral  oils  give  a  very  slight 
rise,  being  paraffines,  while  the  tar  oils  belong  to 
the  benzole  series  and  are  more  easily  nitrated. 
Hydrocarbon  oils  from  distilled  grease  oleines  can 
be  identified  by  their  refractive  index  and  rotatory 
power,  p.  145. 

Solid  unsaponifiable  matters  may  be: 

(4)  Paraffine,  p.  102. 

(5)  Ceresene — refined  ozokerite. 

(6)  Higher  alcohols    of    the    paraffine    series,   as 
cetyl,  C16H33OH,  coming  from  the  saponification  of 
sperm  oil  and  other  waxes. 

(7)  Cholesterol,  C26H43OH,  and   its   isomers,  phy- 
tosterol,  sitosterol,  isocholesterol,  etc. 

(8)  Lactones,  internal  anhydrides  of  oxy  acids,  as 
stearlactone, 
C14H28CHOHCH2CH2COOH  =  C14 

+  H20. 

These  may  be  separated  by  boiling  for  two 
hours  with  an  equal  quantity  of  acetic  anhydride; 
if  the  substance  dissolves  and  does  not  precipitate 
on  cooling,  higher  alcohols  are  indicated;  if  a 
mass  of  crystals  separates  out  on  cooling,  cho- 
lesterol and  its  isomers,  or  a  mixture  of  these  with 
the  higher  alcohols  is  indicated;  if  an  oily  layer 
remains  on  top,  it  is  an  indication  of  the  presence 
of  paraffine  or  ceresene.  For  the  complete  separa- 
tion and  identification  of  these  reference  must  be 
had  to  Lewkowitsch,  "  Analysis  of  Fats,  Oils,  and 
Waxes, "  as  it  is  beyond  the  limits  of  this  volume. 


72  PHYSICAL  AND  CHEMICAL  TESTS. 

SPECIAL  TESTS  FOR  CERTAIN  OILS. 

Lewkowitsch1  states  that  little  reliance  can  be 
placed  upon  the  color  reactions  of  the  various 
oils,  an  opinion  in  which  the  writer  can  cordially 
concur;  with  the  exception  of  the  Bechi,  Baudouin, 
and  Halphen  tests,  in  the  majority  of  cases  with 
a  doubtful  sample  the  doubt  will  still  exist  after 
the  color  test  has  been  performed. 

Bechi's  Test  for  Cotton-seed  Oil.  — This  depends 
upon  the  supposition  that  a  substance  of  an  aldehy- 
dic  nature  which  reduces  silver  nitrate  is  contained 
in  the  oil.  The  method  is  essentially  that  of  Milliau.2 

Fifteen  grams  of  oil  are  weighed  into  a  No.  6  por- 
celain dish,  using  the  coarse  scales,  and  heated  for 
about  ten  minutes  upon  the  water-bath;  a  mixture 
of  ten  cubic  centimeters  of  thirty  per  cent,  caustic 
soda  and  ten  cubic  centimeters  of  the  alcohol  is 
slowly  poured  upon  the  oil.  The  whole  is  occasion- 
ally stirred  until  the  mass  becomes  clear  and  homo- 
geneous, and  one  hundred  and  fifty  cubic  centimeters 
of  hot  distilled  water  slowly  added  so  as  not  to  de- 
compose the  soap,  and  the  boiling  continued  until 
the  alcohol  is  expelled.  Dilute  sulphuric  acid  (1:10) 
is  added  to  acid  reaction,  and  the  separated  fatty 
acids  washed  three  times  by  decantation  with  cold 
water.  A  portion  of  these  is  brought  into  a  large 
test-tube,  fifteen  cubic  centimeters  of  alcohol  and 
two  cubic  centimeters  of  three  per  cent,  silver 


1  J.  Soc.  Chem.  Ind.,  13,  617  (1894). 
3  J.  Am.  Chem.  Soc.,  15,  164  (1893). 


ANIMAL  AND  VEGETABLE  OILS.  73 

nitrate  solution  are  added,  the  tube  is  wrapped 
with  brown  paper,  held  in  place  by  an  elastic  band, 
and  heated,  with  constant  stirring,  in  the  water- 
bath  until  one-third  of  the  alcohol  is  expelled, 
which  is  replaced  by  ten  cubic  centimeters  of 
water.  This  heating  is  continued  for  a  few  min- 
utes longer  and  the  coloration  of  the  insoluble 
fatty  acids  observed.  The  presence  of  cotton-seed 
oil  in  any  appreciable  proportion  causes  a  mirror- 
like  precipitate  of  metallic  silver,  which  blackens 
the  fatty  acids  of  the  mixture. 

Notes. — The  alcohol  should  be  proved  free  from 
aldehyde  by  a  blank  test.  Unless  the  mixture  in 
the  test-tube  be  thoroughly  stirred  while  heating,  it 
will  "  bump  "  and  eject  the  contents.  Other  methods 
of  procedure  consist  in  applying  the  test  to  the  oil 
itself,  often  after  treatment  with  dilute  caustic  soda 
and  nitric  acid.  (Wesson.1)  The  writer  had  a  case  in 
which  the  oil  gave  the  test  while  the  fatty  acids  gave  no 
blackening,  showing  there  was  something  in  the  oil 
itself  other  than  cotton-seed  oil  which  reduced  the 
silver  nitrate.  Students  have  no  difficulty  in  detecting 
a  five  per  cent,  adulteration  with  cotton-seed  oil. 

Dupont 2  thinks  that  the  reduction  of  silver  ni- 
trate is  due  rather  to  sulphur  compounds  contained 
in  the  oil ;  by  passing  steam  over  the  oil  he  obtained 
a  product  containing  sulphur  and  the  oil  still  gave 
the  Bechi  test.  This  work  has  been  repeated  and 

1 J.  Am.  Chem.  Soc.,  17,  723  (1895). 

aBull.  Soc.  Chem.  (3),  13,  696;  J.  Soc.  Chem.  Ind.,  14,  811 
(1895);  also  Charabot  and  March,  Bull.  Soc.  Chim.,  21,  252  (1899). 


74  PHYSICAL  AND  CHEMICAL  TESTS. 

confirmed  by  the  author.1  It  is  to  be  noted  that 
while  the  fatty  acids  blacken  silver  nitrate  they  do 
not  color  cadmium,  lead,  or  copper  salts,  but  reduce 
mercury  compounds.  No  indication  of  an  aldehyde 
was  noted  by  the  fuchsine  or  ammonia  tests.  The 
supposition  that  the  reducing  substance  is  aldehydic 
in  its  nature  finds  support  in  the  fact  that  if  the 
oil  be  heated  to  240° 2  or  be  kept  for  some  time3 
it  loses  this  peculiar  property. 

By  purifying  the  acids  by  the  lead  salts  Tortelli 
and  Ruggeri 4  are  able  to  detect  as  little  as  ten  per 
cent,  of  heated  cotton-seed  oil. 

Halphen's  Test  for  Cotton-seed  Oil.5 — This  depends 
upon  the  observation  that  this  oil  contains  an  un- 
saturated  fatty  acid  which  combines  with  sulphur; 
giving  a  colored  compound.6 

Procedure. — Ten  cubic  centimeters  of  the  oil  or 
melted  fat  are  heated,  in  a  large  test-tube  with  a  long 
glass  condenser  tube  attached,  with  an  equal  volume 
of  amyl  alcohol  and  of  carbon  bisulphide  solution 
of  sulphur  (Reagents),  at  first  with  frequent  agi- 
tation, in  a  steam-bath,  and  then,  after  the  violent 
boiling  has  ceased,  in  a  brine  bath  (105°-110°) 
for  forty-five  minutes  to  three  hours,  according 
to  the  quantity  of  adulterant  present,  the  tube 
being  occasionally  removed  and  shaken.  As  little 

1  Gill  and  Dennison,  J.  Am.  Chem.  Soc.,  24,  397  (1902). 

2  Holde,  J.  Soc.  Chem.  Ind.,  1 1,  637  (1892). 

3  Wilson,  Chem.  News,  59,  99  (1889). 
*  J.  Soc.  Chem.  Ind.,  20,  753  (1901). 

5  Halphen,  J.  Pharm.  Chim.  (1897),  390. 
8  Raikow,  Chem.  Ztg.,  24,  562,  583  (1900). 


ANIMAL  AND  VEGETABLE  OILS.  75 

as  one  per  cent,  will  give  a  crimson  wine  coloration 
in  twenty  minutes.1 

Notes. — If  the  mixture  be  heated  for  too  long  a 
time  a  misleading  brownish-red  color  due  to  burning 
is  produced.  The  reaction  seems  to  be  peculiar  to 
this  oil;  it  is  more  sensitive  with  fresh  than  old 
fats,  and  while,  by  comparison  with  a  blank,  one- 
sixteenth  of  one  per  cent,  is  noticeable,  one-fourth 
of  one  per  cent,  is  easily  detected.  Cotton-seed  oil 
which  has  been  heated  to  250°  does  not  give  the 
test;  the  oil  is  then  not  available  as  food.  Heating 
to  200°  does  not  interfere  with  the  test.2'3 

The  test  is  not  given  by  an  oil  which  has  been 
oxidized  with  sulphuric  acid  and  potassium  per- 
manganate, although  such  an  oil  gives  the  Bechi 
test.4  This  shows  that  the  two  tests  are  not  pro- 
duced by  the  same  substance.  Nor  is  this  test  or 
that  of  Bechi  given  by  an  oil  which  has  been  treated 
with  chlorine  or  sulphurous  acid.5  If  treated  with 
the  former  it  is  no  longer  edible;  an  oil  treated 
with  sulphurous  acid  and  washed  with  alcohol  can- 
not be  distinguished  from  ordinary  cotton-seed  oil 
and  does  not,  as  already  stated,  respond  to  either  the 
Halphen  or  Bechi  test.  In  this  case  the  test  for 
phytosterol  is  the  only  means  of  determining  if  it 
has  been  added  to  an  animal  oil. 

1  Oilar,  Am.  Chem.  J.,  24,  355;   abstr.  Anal.,  26,  22  (1901). 

2  Fischer  and  Peyan,  Analyst,  30,  131  (1905). 

3Soltsien,  Z.  Offentl.  Chem.,  5,  135  (1899);  J.  Soc.  Chem.  Ind., 
18,  865. 

4  Raikow,  loc.  cit. 

»  Petkow,  Analyst,  32,  123  (1907). 


76  PHYSICAL  AND  CHEMICAL  TESTS. 

Lard  from  hogs  fed  on  cotton-seed  meal  shows 
this  reaction  strongly,  as  if  it  were  twenty-five  per 
cent,  oil.1  The  butter  from  cows  similarly  fed  also 
yields  the  reaction.2 

The  test  may  be  applied  to  the  soaps  or  fatty 
acids,  provided  they  are  not  too  deeply  colored. 

The  amyl  alcohol  cannot  be  omitted  nor  substi- 
tuted by  ethyl  alcohol  without  impairing  the  deli- 
cacy of  the  test.3  The  compound  in  the  oil  cannot 
be  removed  by  treatment  with  animal  charcoal.4 

Baudouin's,  or  really  Camoin's,  test  for  Sesame  Oil. 
— Villavecchia  and  Fabris5  apply  the  test  as  fol- 
lows: 0.1  gram  sugar  is  dissolved  in  ten  cubic  cen- 
timeters of  hydrochloric  acid  of  specific  gravity  1.18 
in  a  test-tube  and  twenty  grams  of  the  oil  to  be  tested 
added,  the  whole  thoroughly  shaken  and  allowed  to 
stand.  In  the  presence  of  one  per  cent,  of  sesame  oil 
the  aqueous  liquid  will  be  colored  red,6  due  to  the 
action  of  the  f urfurol  formed  upon  the  oil.  They  state 
that  as  olive  oils  of  undoubted  purity  have  shown 
the  reaction  in  the  aqueous  layer  and  not  in  the  oily 
stratum,  the  color  should  be  looked  for  in  the  latter. 

The  sugar  may  be  replaced  by  0.1  cubic  centi- 
meter of  a  two  per  cent,  solution  of  furfurol  and 
half  the  quantity  of  oil  used. 

1  Soltsien,  Z.  offentl.  Chem.,  7,  140  (1901). 
3  Wauters,  J.  Soc.  Chem.  Ind.,  19,  172  (1900). 
8  Soltsien,  loc.  cit.,  25,  Oilar,  loc.  cit. 
4Utz,  Rev.  Fett.-Harz.-Ind.,  9,  125  (1902). 
•  Z.  angew.  Chem.,  509  (1892);  abstr.  J.  Soc.  Chem.  Ind.,  12,  67; 
also  Kerp,  Analyst,  24,  246  (1899). 

"Ibid.  (1893),  505;  abstr.  Analyst,  19,  47. 


ANIMAL  AND  VEGETABLE  OILS.  77 

Milliau  *  saponifies  as  in  the  Bechi  test  and  dries 
the  acids  at  105°.  Lewkowitsch2  states  that  this  is 
a  needless  complication.  Da  Silva3  states  that  this 
test  has  given  colors  with  certain  Portuguese  olive 
oils.  Kreis4  states  that  the  active  or  color-giving 
constituent  is  probably  phenolic  in  its  nature.  The 
reaction  is  given  by  other  substances,5  as  vanillin,  oil 
of  cloves,  and  cinnamon;  this  should  be  borne  in  mind 
in  testing  oils  which  have  been  extracted  from  confec- 
tionery. Rancid  fats  prevent  the  coloration;  it  can, 
however,  be  brought  about  even  in  rancid  fats  by 
the  addition  of  an  equal  quantity  of  cotton-seed  oil.8 

Bach's  Test. — According  to  0.  Bach,7  the  acids 
obtained  from  rape-seed  oil  are  completely  insoluble 
in  David's  alcoholic  acetic  acid,  in  the  proportion 
of  one  to  fifteen,  by  volume;  those  from  cotton- 
seed, peanut,  sesame,  and  sunflower  oil  dissolve  on 
heating.  Those  from  the  last  oil  separate  as  a 
granular  precipitate  at  15°,  while  from  the  other 
three  they  gelatinize.  The  acids  from  olive  oil  are 
completely  soluble  at  the  ordinary  temperature. 
David's  acid  is  made  by  mixing  twenty-two  cubic 
centimeters  of  fifty  per  cent,  acetic  acid  (by  volume) 
with  thirty  cubic  centimeters  of  alcohol,  sp.  gr. 
0.817,  92.07  per  cent,  (by  weight). 


1  J.  Am.  Chem.  Soc.,  15,  162  (1893). 
'"Oils,  Fats,  and  Waxes." 

3  J.  Soc.  Chem.  Ind.,  17,  275  (1898). 

4  Chem.  Ztg.,  27,  316  (1903). 
5Gerber,  Analyst,  32,  90,  (1907). 

9  Lauff  and  Hinsmann,  Chem.  Ztg.,  31,  1023  (1908). 

7  Allen, "Commercial  Organic  Analysis, ' '  vol.  ii.,  pt.  1,  p.  128  (1899). 


78 


PHYSICAL  AND  CHEMICAL  TESTS. 


FIG.  6, 


Notes.— The  author  has  found  that  Bach's  obser- 
vation cannot  be  implicitly  relied  upon,  as  some 
rape-seed  oils  yield  acids  which  are  soluble  in 
David's  mixture. 

Free  Acid  Test. — About  ten  grams  of  oil  are  weighed 
(to  centigrams)  into  a  250  cubic  centimeter  Erlen- 
meyer  flask,  sixty  cubic  centimeters 
of  neutral  alcohol  (Reagents)  added, 
the  mixture  warmed  to  about 
60°  C.,  and  titrated  with  £  potas- 
sium hydrate,  using  phenolphtha- 
lein,  the  flask  being  frequently 
and  thoroughly  shaken.  The  result 
is  conventionally  reported  in  per 
cent,  of  oleic  acid;  1.0  cubic  centi- 
meter §  KOH  is  equivalent  to  0.047 
gram  oleic  acid. 

Spontaneous  Combustion  Test. — 
Mackey's  Apparatus. — The  appa- 
ratus,1-2 Fig.  6,  consists  of  a  cylin- 
drical copper  water-bath  7  inches 
high  and  4  inches  in  diameter  (inside 
measurements),  surrounded  with  a  half-inch  water- 
jacket.  The  cover  is  packed  with  asbestos  and  carries 
the  draft  tubes  A  and  B,  \  inch  in  diameter  and  6 
inches  long,  which  cause  a  current  of  air  to  be  sucked 
down  B  and  up  A,  thus  ensuring  a  circulation  of  air 
in  the  apparatus:  C  is  a  cylinder  made  of  24-mesh 
wire  gauze  6  inches  high  and  1J  inches  in  diameter 


Mackey's  apparatus. 


1Mackey,  J.  Soc.  Chem.  Ind.,  15,  90  (1896). 
'Gill,  id.,  26,  185(1907). 


ANIMAL  AND  VEGETABLE  OILS.  79 

and  supported  upon  a  projection  from  the  bottom  of 
the  bath.  A  thermometer  projects  down  into  the 
center  of  the  cylinder;  if  a  metal  condenser  be  con- 
nected to  the  water-bath  it  can  be  used  indefinitely 
without  refilling  and  without  danger  of  burning  out. 
Seven  grams  of  ordinary  bleached  cotton  wadding 
are  weighed  out  in  a  porcelain  dish  or  on  a  watch- 
glass,  and  14  grams  of  the  oil  to  be  tested  poured 
upon  the  cotton  and  thoroughly  worked  into  it,  care 
being  taken  to  replace  any  oil  that  is  lost.  The 
cotton  is  then  placed  in  the  cylinder,  packed  about 
the  thermometer  so  that  it  occupies  the  upper  4J 
inches  of  the  cylinder,  and  put  into  the  boiling 
water-bath.  After  the  expir'ation  of  an  hour,  the 
bath  having  been  kept  in  active  ebullition,  the  tem- 
perature is  read.  Any  oil  which  shows  a  temperature 
exceeding  100°  C.  in  one  hour  or  200°  C.  in  two  hours 
should  be  regarded  as  a  dangerous  oil,  or  liable  to  pro- 
duce spontaneous  combustion.  The  following  tables 
show  the  results  obtained  in  using  this  apparatus. 

Temperature  °C.  in 
Oil  Ihr.  IJhrs.  1*  hrs. 

Olive  (neutral) 97-98  100  101 

Cotton-seed 112-128  177-242  194-282 

Elaine 98-103  101-115  102-191 

Olive  fatty  acids 102-114  196 

Other  values  obtained  were : 

Temp.       Time          Iodine       Free  Acid 
Oil  °C.        Minutes  No.         per  cent. 

Olive 234  130  85.4  5.3 

Lard 234  75  75.2  Trace 

OleicAcid 158  188  60.5  

Cotton-seed 234  70  108.9  Neutral 

Linseed 234  65  168.1  Neutral 

25°  Paraffin..                 97  135  16.2  


80  PHYSICAL  AND  CHEMICAL  TESTS. 

Besides  being  used  for  testing  oils  it  can  be  applied 
to  testing  other  materials,  oily  waste,  sawdust,  or  any 
mixture  suspected  of  causing  spontaneous  combustion. 

Other  apparatus,  particularly  that  of  Ordway,1 
described  in  earlier  editions  of  this  book,  while 
giving  trustworthy  results,  has  not  been  found  to 
give  such  rapid  and  concordant  results  as  are 
obtained  with  Mackey's. 

For  an  account  of  early  experiments  along  this 
line  reference  may  be  had  to  papers  by  Coleman  and 
Dollfus  in  the  Bulletin  of  the  Industrial  Society  of 
Mulhouse,  1875  and  1876. 

"The  results1  of  the  greatest  practical  value  ob- 
tained in  the  use  of  this  apparatus  have  been,  first, 
determining  the  cause  of  fires;  and,  second,  deter- 
mining the  degree  of  safety  of  the  various  oils  used 
in  manufacturing.  Mineral  oil,  as  is  well  known,  is 
not  liable  to  spontaneous  combustion;  and  a  certain 
percentage  of  animal  or  vegetable  oil  may  be  added 
to  mineral  oil  without  materially  increasing  the 
danger  under  ordinary  circumstances.  This  per- 
centage varies  according  to  the  oil;  with  neat's- 
foot  and  first  quality  lard  oil  some  fifty  to  sixty 
per  cent,  may  be  used,  with  cotton-seed  not  over 
twenty-five  per  cent,  is  allowable.  The  claim  so 
often  made  for  so-called  'safe'  oils,  said  to  have 
been  changed  by  special  and  secret  processes  of 
refining  so  as  to  be  no  longer  dangerous,  is  easily 
exposed  by  this  test." 

1  Richards,  Tech.  Quarterly,  4,  346  (1891). 


ANIMAL  AND  VEGETABLE  OILS.  81 

Drying  Test. — This  is,  as  would  be  implied,  more 
especially  applicable  to  the  drying  oils;  there  are  two 
ways  of  applying  it,  exposure  of  the  oil  upon  finely 
divided  lead  (Livache  test)  and  upon  a  plate  of  glass. 

Livache  Test.1 — One  gram  of  precipitated  lead  is 
spread  out  in  a  thin  layer  on  a  three-inch  flat  watch- 
glass  and  accurately  weighed;  0.5  to  0.6  gram  of 
the  oil  (twenty  to  twenty-four  drops)  are  brought 
upon  the  lead  from  a  pipette,  taking  care  that  the 
drops  do  not  touch  each  other,  the  watch-glass  and 
contents  again  accurately  weighed,  and  exposed 
to  light  and  air  at  ordinary  temperature.  It  is 
weighed  from  time  to  time,  the  maximum  weight 
being  reached  in  from  eighteen  to  seventy-two  hours. 
The  oil  that  increases  most  in  a  given  time  is 
considered  to  be  the  best  drying  oil. 

Lippert 2  confirms  Weger's  opinion  that  the 
Livache  test  as  here  carried  out  is  unreliable  and 
advises  the  use  of  copper  powder  instead  of  lead. 
This  is  known  as  "cement  copper,"  and  is  prepared 
similarly  to  the  precipitated  lead. 

Test  upon  Glass.3 — A  few  drops  of  the  oil  are  brought 
upon  a  glass  plate  inclined  at  about  thirty  degrees 
from  the  horizontal.  A  test  of  the  oil  is  made  from 
time  to  time  by  touching  it  with  the  fingers,  the  time 
at  which  it  does  not  soil  them  being  noted  as  the  point 
when  it  is  dry.  Good  oil  should  dry  in  three  days. 

1  Compt.  rend.,  102,  1167  (1886). 

2Rev.Fett.-Harz.-Ind.,  6,  65;  abstr.  J.  Soc.  Chem.  Ind.,  18,  693 
(1899). 

3  Amsel,  J.  Soc.  Chem.  Ind.,  15,  222  (1896). 


82  PHYSICAL  AND  CHEMICAL  TESTS. 

Archbutt *  makes  this  test  as  follows :  A  piece 
of  polished  plate-glass  seven  centimeters  square  by 
four  millimeters  thick  is  cleaned  and  counterpoised 
on  the  balance;  it  is  then  heated  for  an  hour  at 
200°  C.  in  an  air-bath  to  thoroughly  dry  it.  It  is 
taken  out,  laid  on  a  non-conductor,  allowed  to  cool 
for  three  or  four  minutes,  and  the  hot  glass  thinly 
painted  with  the  oil  to  be  tested  by  means  of  a 
camel's-hair  brush.  When  the  glass  is  cold  it  is 
weighed  and  sufficient  oil  added  to  make  it  up  to 
0.1  gram.  Two  glasses  are  coated  with  the  sample 
and  two  with  a  standard  oil,  all  placed  on  a  level 
surface  in  a  large  air-bath  at  50°  C.  and  heated  for 
nine  hours;  one  set  of  plates  is  withdrawn,  cooled, 
and  tested  by  the  finger.  Good  raw  linseed  is 
tacky,  when  tested  by  the  finger  when  cold,  in  nine 
hours  and  dry  in  twelve;  corn  oil  is  practically 
dry  in  fifteen  hours,  though  slightly  tacky;  cotton- 
seed, partially  dry  in  eighteen  hours  and  fully  dry 
in  twenty-one.  Refined  rape  oil  dried  in  forty-eight 
hours,  and  olive  oil  was  sticky  after  thirteen  days. 

Titer  Test. — Under  this  rather  misleading  title  is 
expressed  the  solidification  point  of  the  fatty  acids 
derived  from  a  fat  or  oil;  it  has  nothing  at  all  to  do 
with  titration,  as  might  be  expected.  The  test  is 
extensively  used  for  the  evaluation  of  fats,  and 
according  to  the  method  provisionally  adopted  by 
the  Association  of  Official  Agricultural  Chemists  is 
carried  out  as  follows:2 

» J.  Soc.  Chem.  Ind.,  18,  347  (1899). 

2  U-  S.  Dept.  of  Agriculture,  Bureau  of  Chemistry  Bulletin  No. 
107,  p.  135  (1907). 


ANIMAL  AND  VEGETABLE  OILS.  83 

(a)  STANDARD  THERMOMETER. 
The  thermometer  must  be  graduated  in  tenth 
degrees  from  10°  to  60°,  with  a  zero  mark,  and  have 
an  auxiliary  reservoir  at  the  upper  end,  also  one 
between  the  zero  mark  and  the  10°  mark.  The 
cavity  in  the  capillary  tube  between  the  zero  mark 
and  the  10°  mark  must  be  at  least  1  cm.  below  the 
10°  mark,  the  10°  mark  to  be  about  3  or  4  cm. 
above  the  bulb,  the  length  of  the  thermometer  being 
about  15  inches  over  all.  The  thermometer  is 
annealed  for  75  hours  at  450°  C.,  and  the  bulb  is  of 
Jena  normal  16"'  glass,  moderately  thin,  so  that  the 
thermometer  will  be  quick  acting.  The  bulb  is 
about  3  cm.  long  and  6  mm.  in  diameter.  The  stem 
of  the  thermometer  is  6  mm.  in  diameter  and  made 
of  the  best  thermometer  tubing,  with  scale  etched 
on  the  stem,  the  graduation  to  be  clear-cut  and 
distinct,  but  quite  fine. 

(b)   DETERMINATION. 

Saponify  75  grams  of  fat  in  a  metal  dish  with  60 
cc.  of  30  per  cent,  sodium  hydroxid  (36°  Baume") 
and  75  cc.  of  95  per  cent,  (by  volume)  alcohol  or 
120  cc.  of  water.  Boil  to  dryness,  with  constant 
stirring  to  prevent  scorching,  over  a  very  low  flame 
or  over  an  iron  or  asbestos  plate.  Dissolve  the  dry 
soap  in  a  liter  of  boiling  water,  and  if  alcohol  has 
been  used,  boil  for  forty  minutes  in  order  to  remove 
it,  adding  sufficient  water  to  replace  that  lost  in 
boiling.  Add  100  cc.  of  30  per  cent,  sulphuric  acid 


84  PHYSICAL  AND  CHEMICAL  TESTS. 

(25°  Baume*)  to  free  the  fatty  acids,  and  boil  until 
they  form  a  clear,  transparent  layer.  Wash  with 
boiling  water  until  free  from  sulphuric  acid,  collect 
in  a  small  beaker,  and  place  on  the  steam  bath  until 
the  water  has  settled  and  the  fatty  acids  are  clear; 
then  decant  them  into  a  dry  beaker,  filter,  using  the 
hot-water  funnel,  and  dry  twenty  minutes  at  100°  C. 
When  dried,  cool  the  fatty  acids  to  15°  or  20°  C. 
above  the  expected  titer  and  transfer  to  the  titer 
tube,  which  is  25  mm.  in  diameter  and  100  mm.  in 
length  (1  by  4  inches)  and  made  of  glass  about  1  mm. 
in  thickness.  Place  in  a  16-ounce  saltmouth  bottle 
of  clear  glass,  about  70  mm.  in  diameter  and  150  mm. 
high  (2.8  by  6  inches),  fitted  with  a  cork,  which  is 
perforated  so  as  to  hold  the  tube  rigidly  when  in 
position.  Suspend  the  thermometer,  graduated  to 
0.1°  C.,  so  that  it  can  be  used  as  a  stirrer,  and  stir 
the  mass  slowly  until  the  mercury  remains  station- 
ary for  thirty  seconds.  Then  allow  the  thermometer 
to  hang  quietly,  with  the  bulb  in  the  center  of  the 
mass,  and  observe  the  rise  of  the  mercury.  The 
highest  point  to  which  it  rises  is  recorded  as  the 
titer  of  the  fatty  acids. 

Test  the  fatty  acids  for  complete  saponification 
as  follows: 

Place  3  cc.  in  a  test-tube  and  add  15  cc.  of  alcohol 
(9$  per  cent,  by  volume).  Bring  the  mixture  to  a 
boil  and  add  an  equal  volume  of  ammonium  hy- 
droxid  (0.96  sp.  gr.).  A  clear  solution  should  result, 
turbidity  indicating  unsaponified  fat.  The  titer 
must  be  made  at  about  20°  C.  for  all  fats  having  a 


ANIMAL  AND  VEGETABLE  OILS.  85 

liter  above  30°  C.  and  at  10°  C.  below  the  titer  for 
all  other  fats. 

REFERENCES. 

HEFTER,  G.  Technologie  der  Fette,  Oele,  und  Wachsarten  des 
Pflanzen  und  Tierreichs.    4  volumes,  1906  + 

UBBELOHDE,  L.  Chemie,  Analyse  und  Gewinnung  der  Oele,  Fette 
und  Wachse.    4  volumes,  1908  + 


CHAPTER  IV. 

GENERAL  CONSIDERATIONS  REGARDING  LUBRICANTS. 

Method  of  Examination  of  an  Unknown  Oil. 

ACCORDING  to  the  results  of  the  viscosity  and 
friction  tests,  the  least  viscous  oil  is  to  be  given  the 
preference.  It  should  be  borne  in  mind,  however, 
that  the  heat  of  the  journal  diminishes  the  viscosity: 
for  example,  at  60°  F.,  if  the  viscosity  of  sperm  oil 
be  taken  as  100,  that  of  25°  paraffine  oil  is  123;  at 
100°  F.  the  latter  has  diminished  to  110,  and  at 
250°  F.  they  are  practically  equal.  On  account  of 
this  change  in  temperature,  as  well  as  the  irregulari- 
ties of  the  journals,  of  the  feed,  and  of  pressure,  a 
too  thinly  fluid  oil  must  not  be  chosen. 

The  following  considerations  will  aid  in  the 
selection  of  a  suitable  oil. 

1.  The  flashing  point  of  the  oil  should  be  above 
300°  F. 

2.  The  oil  should  have  an  evaporation  test  of  less 
than  five  per  cent. 

3.  On  general  principles  the  most  fluid  oil  that 
will  stay  in  place  should  be  used. 

4.  The  best  oil  is  that  which  possesses  the  greatest 
adhesion  and  least  cohesion.    This  condition  is  ful- 
filled, first,   by  fine  Mineral  Oils;1  second,  Sperm; 
third,  Neat's-foot;  fourth,  Lard. 

1  Except  at  high  temperatures.    Doolittle,  J.  Am.  Chem.  Soc., 
20,  238  (1898). 
86 


LUBRICANTS:   GENERAL  CONSIDERATIONS.         87 

5.  For  light  pressures  and  high  speeds,  Mineral 
Oils  of  specific  gravity  30.5°  Be.,  flash  point  360° 
F.,  Sperm,   Olive,  and  Rape   (Thurston  adds  also 
Cotton-seed),  should  be  employed. 

6.  For  ordinary  machinery,  Mineral  Oils  of  spe- 
cific gravity  25°  to  29°  B<§.,  flash  point  400°  to  450° 
F.,  Lard,  Whale,  Neat's-foot,  and  Tallow,  also  heavy 
Vegetable  Oils,  should  be  used. 

7.  For  cylinder  oils,  Mineral  Oils  of  specific  gravity 
27°  Be".,  flash  point  550°  F.,  alone  and  with  small 
percentages  (1  to  7)  of  Animal  or  Vegetable  Oils, 
are  employed;    the  latter  are  Degras,  Tallow,  Lin- 
seed, Cotton-seed,  and  blown  Rape. 

8.  For  watches  and  clocks,  clarified  Sperm,  Jaw, 
and  " Melon"  oils  should  be  employed. 

9.  For    heavy    pressure    and    slow   speed,    Lard, 
Tallow,  and  other  greases,  either  by  themselves  or 
mixed    with    Graphite    and    Soapstone,   should   be 
used. 

10.  For  very  heavy  pressure,  solid  lubricants,  as 
Graphite  and  Soapstone,  are  employed. 

11.  To  resist  cold,  as,  for  example,  for  lubricating 
air-driven  rock-drills,  Kerosene  has  been  used. 

12.  The  oil  should    contain   no   acid  to   corrode 
the  shaft  or  journal;    the  German  railroads  l  per- 
mit no  more  than  0.1  to  0.3  per  cent,  of  acids,  calcu- 
lated as  sulphuric  anhydride,  in  their  oils.     For  the 
action  of  oils  upon  metals  reference  may  be  had  to 
Table  X. 

1Aisinmann,  Z.  angew.  Chemie,  11,  213;  abstr.  J.  Soc.  Chem. 
Ind.,  14,  811  (1895). 


88  PHYSICAL  AND  CHEMICAL  TESTS. 

REFERENCES. 

MILLS,  J.  Soc.  Chem.  Ind.,  5,  148,  149  (1886). 
COLEMAN,  ibid.,  359.    REDWOOD,  idem,  121-132. 
DENTON,  Trans.  Am.  Soc.  Mech.  Engrs.,  9,  369  (1888);   11, 
1013  (1890). 

ARCHBUTT  and  DEELEY,  "  Lubrication  and  Lubricants,"  48-131. 

WM.  M.  DAVIS,  "  Friction  and  Lubrication." 

D.  HOLDE,  "  Untersuchung  der  Mineral  Oele  und  Fette." 

Method  of  Examination  of  an  Unknown  Oil. 

There  being  no  specific  tests  foAhe  different  oils,1 
as  in  the  case  of  the  various  elementary  substances, 
the  analyst  should,  in  attacking  an  unknown  oil, 
ascertain  all  possible  facts  about  it,  as  the  source, 
the  use  to  which  it  is  put,  and  the  cost.  A  low- 
priced  oil  is  not  likely  to  be  adulterated  with  one  of 
higher  cost.  While  the  prices  fluctuate  to  a  consid- 
erable extent,  yet  the  following  table,  it  is  believed, 
represents  the  average  price  of  the  various  oils,  the 
highest  priced  being  given  first: 

1.  Almond.  7.  Sperm.  12.  Lard. 

2.  Castor.  8.  Whale.  13.  Cod. 

3.  Sesame.  9.  Peanut.  14.  Cotton-seed. 

4.  Neat's-foot.  10.  Linseed.  15.  Mineral. 

5.  Rape.  11.  Tallow.  16.  Rosin. 

6.  Olive. 

Certain  physical  properties  may  aid  in  the  exami- 
nation. The  color  is  of  little  assistance,  as  oils  may 
be  colored  by  the  use  of  the  oleates  or  butyrates  of 
iron  or  copper.  Fluorescence  is  valuable  as  indicat- 

1  At  the  present  state  of  our  knowledge  (1908)  we  can  detect  the 
following  oils  with  certainty:  Castor,  Cokernut,  Cotton-seed,  Pea- 
nut, Rosin,  and  Sesame.  We  can  be  reasonably  certain  of  25  per 
cent,  of  Corn,  Rape,  and  Sperm  oils. 


LUBRICANTS:    GENERAL  CONSIDERATIONS. 


ing  the  presence  of  mineral  oil;  this  can  be  shown  by 
placing  a  few  drops  of  the  oil  on  a  sheet  of  ebonite 
and  observing  the  bluish  color. 

The  odor  and  taste,  as  has  already  been  stated, 
may  to  experts  reveal  much  about  the  nature  of 
the  oil  under  examination.  Marine  animal  oils  are 
detected,  especially  when  warm,  by  their  strong 
"fishy"  odor,  while  neat's-foot,  tallow,  lard,  olive, 
rosin,  and  linseed  oils  each  have  a  well-marked  and 
easily  distinguishable  odor.  Whale  oil  has  a  nutty, 
and  rape  oil  a  harsh,  unpleasant  taste. 

The  specific  gravity  should  next  be  noted,  the  oil 
being  exactly  at  15°  C.  The  accompanying  table 
shows  the  groups  into  which  the  oils  are  divided  by 
this  criterion: 


.875-.8S4. 

.884-.912. 

.912-.920. 

.920-.937. 

.937-.970. 

Sperm. 

Oleic  Acid. 

Almond. 
Lard. 
Neat's-foot. 
Olive. 
Peanut. 
Rape. 
Tallow. 

Corn. 
Cotton-seed. 
Fish. 
Linseed. 
Poppy-seed. 
Sesame. 

Castor. 
Blown  Oils. 

The  elaidin  test  (page  51)  may  be  applied  next,  to 
allow  time  for  the  cake  to  form;  it  will  be  followed 
by  the  Valenta  (page  50)  and  Maumene  (page  52) 
tests,  all  of  these  being  done  in  duplicate.  In  mak- 
ing the  elaidin  test,  it  is  advisable  to  carry  on  an 
experiment  under  the  same  conditions  with  a  known 
sample  of  lard  oil. 

From  the  result  of  the  examination  up  to  this 


90  PHYSICAL  AND  CHEMICAL  TESTS. 

time  a  reasonably  good  idea  of  the  nature  of  the 
oil  will  have  been  obtained;  the  iodine  test  can 
now  be  applied  and  the  percentage  of  adulteration 
approximated.  The  data  obtained  by  the  Maumen6 
test  and  specific  gravity  determination  will  serve 
as  checks  upon  this.  In  case  Sesame,  Cotton-seed, 
Peanut,  or  Rosin  oils  be  suspected,  the  specific  tests 
for  them  can  be  made. 

The  saponification  test,  unless  mineral  oil  be  sus- 
pected, need  rarely  be  resorted  to;  the  reason  being 
that  it  would  show  practically  nothing  regarding 
the  nature  of  the  oil.  This  is  evident  from  Table 
VIII.  Of  all  the  oils  there  given,  this  constant, 
excepting  Castor  (181),  Rape  (174),  and  Sperm 
(135),  being  about  193.  Finally,  where  the  impor- 
tance of  the  case  will  warrant,  the  analyst  is  advised 
to  prepare  a  mixture  of  the  oils,  using  the  propor- 
tions indicated  by  the  various  tests,  and  subject  it 
to  the  more  rapid  tests,  as  the  Specific  Gravity, 
Viscosity,  Maumene",  and  Bromine  Number.  It 
should  be  borne  in  mind  in  making  out  the  report 
that,  excepting  in  the  case  of  the  special  tests,  the 
results  of  one  test  cannot  be  relied  upon  to  determine 
the  nature  of  an  oil,  but  the  evidence  of  all  the  tests 
here  given  should  be  carefully  weighed  and  com- 
pared before  rendering  a  final  verdict. 

Test  for  Animal  or  Vegetable  Oils. — Animal  oils 
contain  cholesterol,  C26H43OH,  while  vegetable  oils 
contain  the  isomeric  body  phytosterol;  hence  the 
isolation  and  identification  of  these  compounds 
enables  one  to  say  with  certainty  as  to  the  pres- 


LUBRICANTS:    GENERAL  CONSIDERATIONS.         91 

ence  of  one  class  of  oil  or  the  other — for  example 
as  to  the  presence  of  fish  oil  in  linseed.  The  quan- 
tity of  these  bodies  varies  from  0.2  to  one  per  cent. 
The  method  is  essentially  that  of  Bomer.W  Fifty 
grams  of  the  oil  are  boiled  in  a  flask  with  a  return 
cooler  with  75  cc.  of  95  per  cent,  alcohol  for  five 
minutes  and  the  alcoholic  solution  separated;  this 
is  repeated  with  another  portion  of  alcohol.  The 
alcoholic  solutions  are  mixed  with  15  cc.  of  30 
per  cent,  sodium  hydroxide  and  evaporated  on  a 
water-bath  nearly  to  dryness  in  a  porcelain  dish  and 
the  residue  shaken  out  with  ether.  The  ether  is 
evaporated,  the  residue  taken  up  with  a  little  ether, 
filtered,  again  evaporated,  dissolved  in  95  per  cent, 
alcohol  (by  volume),  and  allowed  to  crystallize 
slowly.  Bomer  states  that  the  form  of  the  crystals 
is  more  to  be  relied  upon  than  a  determination  of 
their  melting  point.  Cholesterol  crystallizes  from 
alcohol  or  ether  in  leaflets  or  rhomboid  tables  con- 
taining one  molecule  of  water  of  crystallization. 
Phytosterol  crystallizes  also  from  alcohol  with  one 
molecule  of  water  in  needles  forming  stars  or  bundles. 
As  a  further  means  of  identification,  some  of  the 
esters  should  be  made  and  their  melting  points 
determined. 

To  this  end  the  crystals  above  obtained  are 
heated  over  a  low  flame  in  a  small  porcelain  dish 
covered  with  a  watch-glass,  with  2  or  3  cc.  of  acetic 

1  J.  Soc.  Chem.  Ind.,  17,  954  (1898). 

'Tolman,  J.  Am.  Chem.  Soc.,  27,  590  (1905). 

3  Tolman,  Bull.  107,  U.  S.  Dept.  Agriculture  (1907). 


92  PHYSICAL  AND  CHEMICAL  TESTS. 

or  other  acid  anhydride  until  it  boils:  the  watch- 
glass  is  removed  and  the  excess  of  anhydride 
evaporated  on  the  water-bath.  The  contents  of  the 
dish  are  treated  with  a  small  quantity  of  absolute 
alcohol  to  prevent  crystallization,  more  alcohol 
added  and  the  solution  allowed  to  crystallize.  The 
crystals  are  filtered  off  through  a  very  small  filter, 
washed  with  a  small  quantity  of  95  per  cent,  alcohol, 
dissolved  in  absolute  alcohol,  and  recrystallized  until 
a  constant  melting  point  is  obtained. 

The  following  table  shows  the  corrected  melting 
points  of  these  alcohols  and  their  esters: 

Cholesterol.  Phytosterol. 

Alcohol 148-150.8°  136-143.8° 

Acetate 113-114°  120-137° 

Benzoate 145-151°  142-148° 

Propionate 97-98°  104-105° 

Notes. — Some  directions  state,  in  isolating  the 
cholesterol  or  phytosterol,  to  boil  with  the  30  per 
cent,  sodium  hydroxide  until  one-fourth  of  the 
alcohol  is  evaporated.  As  a  result  of  repeated 
experiments  this  has  been  found  to  cut  down  the 
yield  so  much  that  on  a  large  scale  practically  none 
of  these  bodies,  particularly  phytosterol,  was  ob- 
tained. This  agrees  with  the  observation  of  Lew- 
kowitsch  that  by  heating  cholesterol  with  normal 
alcoholic  potash,  cholesterin  hydrate  is  obtained. 

The  following  test  will  serve  to  differentiate 
between  cholesterol  and  phytosterol.1  A  very  small 

*Neuberg  and  Rauchwerger,  abstr.  J.  Soc.  Chem.  Ind.,  23, 
1163(1904). 


LUBRICANTS:    GENERAL  CONSIDERATIONS.         93 

quantity  of  cholesterol  is  warmed  with  1.5  cc. 
absolute  alcohol  and  a  trace  of  isodulcit  or  rhamnose 
(^-dimethylfurfural)  added.  After  cooling,  an  equal 
volume  of  concentrated  sulphuric  acid  is  added,  so 
as  to  form  a  layer  below  the  solution,  whereupon  a 
raspberry-colored  ring  is  produced  at  the  zone  of 
contact  of  the  two  liquids.  On  mixing  the  layers 
while  the  tube  is  cooled  in  a  current  of  cold  water 
the  mixture  becomes  intensely  colored.  With  phy- 
tosterol  the  reaction  fails  or  at  most  a  pink  color. 
Similar  reactions  are  given  by  abietic  acid. 

As  little  as  one  per  cent,  of  cotton-seed  has  been 
found  in  lard,  and  four  per  cent,  in  any  oil  have 
been  detected  by  this  test. 

For  the  means  of  distinguishing  between  drying 
and  marine  animal  oils,  see  Halphen,  J.  Pharm. 
Chim.,  14,391  (1901),  abstracted  J.  Soc.  Chem.  Ind., 
21,  74,  or  Chem.  Centralb.,  72,  ii.,  1097  and  1323. 


PART  II. 

DERIVATION,  DESCRIPTION,  AND 
EXAMINATION. 


DERIVATION,  DESCRIPTION,  AND  EXAM- 
INATION OF  CERTAIN  OILS. 


IN  this  part  the  technology  and  properties  of  the 
more  commonly  occurring  oils  will  be  considered 
under  the  following  heads: 

1.  Source  and  Preparation. 

2.  Physical  Characteristics. 

3.  Chemical  Composition. 

4.  Analytical  Constants. 

5.  Adulterations  and  their  Effects. 

6.  Uses. 

The  analytical  data  are  the  average  of  the  results 
from  many  sources;  in  addition  to  these  the  highest 
and  lowest  results  are  often  given. 

The  classification  of  the  animal  and  vegetable 
oils  is  that  of  Lewkowitsch,  following  in  the  various 
groups  of  oils  the  order  of  the  iodine  values. 

A.  Oils  and  Fats.     Glycerides. 

1.  VEGETABLE  OILS. 

(1)  Drying  Oils. 

(2)  Semi-drying  Oils. 

(3)  Non-drying  Oils. 

7  97 


EXAMINATION  OF  CERTAIN  OILS. 

2.  ANIMAL  OILS. 

(1)  Marine  Animal  Oils. 

a.  Fish  Oils. 
0.  Liver  Oils. 
Y.  Blubber  Oils. 

(2)  Terrestrial  Animal  Oils. 

B.  Waxes.    Non-Qlycerides. 

LIQUID  WAXES. 


CHAPTER  V. 

PETROLEUM  PRODUCTS. 

CRUDE  petroleum  varies  so  much  with  the  locality 
that  any  statement  about  it  is  only  approximate; 
according  to  Peckham,1  the  products  which  may  be 
obtained  from  Pennsylvania  petroleum  are  about  as 
follows : 

First.  The  NAPHTHA  DISTILLATE,  all  that  passing 
over  above  60°  Baum6,  about  sixteen  and  five-tenths 
per  cent. 

Second.  The  BURNING  OIL  DISTILLATE,  that  pass- 
ing over  between  60°  and  36°  B6.,  about  fifty-four 
per  cent. 

Third.  The  LUBRICATING  OIL  DISTILLATE,  that 
passing  over  from  36°  to  23°  B6.,  about  seventeen 
and  five-tenths  per  cent. 

Fourth.  PARAFFINE,  two  per  cent. 

Fifth.  COKE  AND  LOSSES,  ten  per  cent. 

The  Naphtha  Distillate. — This  is  fractionated  as 
follows : 

I.  Crude  Gasolene,  cut  at  80°  B6.,  one  and  five- 
tenths  per  cent. 

II.  C  Naphtha,  between  80°  and  68°  B6. ,  ten  per  cent. 

III.  B  Naphtha,  between  68°  and  64°  B6.,  two  to 
two  and  five-tenths  per  cent. 

1S.  F.  Peckham,  'Report  on  Petroleum,"  p.  165;  also  J.  Soc. 
Chem.Ind.,  13,794(1894). 

99 


100  EXAMINATION  OF  CERTAIN  OILS 

IV.  A  Naphtha,  between  64°  and  60°  Be.,  two  to 
two  and  five-tenths  per  cent. 

Fraction  I.  is  redistilled  and  the  products  caught 
in  a  mixture  of  ice  and  salt,  giving:1 

1.  Cymogene,  110°  to  100°  Be.,  Bpt.  32°  F.,  largely 
butane,  used  for  ice-machines. 

2.  Rhigolene,  100°  to  90°  Be.,  Bpt.  65°  F.,  largely 
pentane,  used  as  a  local  anaesthetic. 

3.  Petroleum   Ether,   Sherwood    Oil,   "  Gasolene," 
90°  to  80°  Be.,  Bpt.  100°  to  150°  F.,  largely  hexane, 
used  for  carburetting  air  in  the  various  "  gas-ma- 
chines" and  in  the  laboratory  for  oil  and  fat  ex- 
traction. 

4.  Gasolene,  Canadol,  80°  to  75°  Be.,  Bpt.   150° 
to  190°  F.,  used  for  oil  extraction  on  the  large  scale. 

Fraction  II.  is  treated  with  four  ounces  of  oil  of 
vitriol  to  the  gallon  in  an  agitator  with  mechanical 
paddles,  washed  with  caustic  soda  solution,  and  dis- 
tilled with  steam,  yielding: 

5.  Naphtha,  Danforth's  Oil,  76°  to  70°  Be.,  Bpt. 
160°  to  210°  F.,  used  in  street  lamps,  stoves,  torches, 
and  gasolene  engines. 

Fractions  III.  and  IV.  are  treated  similarly  to  II., 
giving: 

6.  Ligroine,  67°  to  62°  Be.,  Bpt.  160°  to  225°  F.,2 
used  in  pharmacy,  in  the  laboratory,  and  in  sponge 
lamps. 

7.  Benzine  (deodorized),  62°  to  57°  Be.,  Bpt.  225° 

1  Sadtler,  "Industrial  Organic  Chemistry"  (1895),  p.  30. 

2  Freezing   point,  — 147°  C.     Cabot,  J.   Soc.  Chem.  Ind.,  26, 
813  (1907). 


PETROLEUM  PRODUCTS.  101 

to  300°  F.,  used  as  a  substitute  for  turpentine,  for 
cleaning  type,  and  by  dyers  and  scourers. 

The  Burning  Oil  Distillate. — This  is  fractionated 
into : 

V.  Crude  Burning  Oil,  58°  to  40°  Be.,  forty-two 
per  cent. 

VI.  "B"  Oil,  40°  to  36°  Be.,  seventeen  per  cent. 
Fraction  V.  is  treated  with  acid  similarly  to  II., 

washed,  and  distilled  as  long  as  the  color  is  good. 
Three  fractions  may  be  obtained: 

8.  " Export    Oil,"    110°   F.,    Fire   Test    (F.   T.), 
shipped  to  China  and  Japan. 

9.  Export  Oil,  120°  F.,  F.  T.,  shipped  to  England. 

10.  Headlight  Oil,  150°  F.,  F.  T.,  50°  to  47°  Be., 
ordinary  kerosene. 

Fraction  VI.  is  treated  similarly  to  V.,  and  on 
distillation  yields: 

11.  Mineral    Sperm,    or    Lantern    Oil,    36°    Be., 
250°  F.,  Flash  point,  and  300°  F.,  F.  T.,  used  for 
passenger  traffic  illumination  and  in  light-houses. 

The  Lubricating  Oil  Distillate. — The  residues  from 
the  burning  oil  distillate  are  distilled  with  super- 
heated steam,  various  fractions  being  obtained; 
these  are  treated  with  acid,  washed,  and  redistilled, 
yielding : 

" Neutral"  Oils,  38°  to  32°  Be.,  used  as  "wool 
oils." 

Spindle  Oils,  32°  to  28°  Be\ 

Loom  Oils,  29°  to  27°  Be*. 

Engine  Oils,  27°  to  23°  Be\ 

Cylinder  Oils,  28°  to  25°  Be\ 


102  EXAMINATION  OF  CERTAIN  OILS. 

These  fractions  are  filtered  through  sawdust  and 
salt  to  remove  water,  and  when  too  deeply  colored 
through  bone  charcoal,  after  the  manner  of  sugar 
syrups. 

In  addition  to  these  distilled  oils  there  is  another 
class,  the  paraffine  oils,  which  are  obtained  by  chill- 
ing and  pressing  certain  distillates,  yielding  solid 
paraffine  and  paraffine  oil. 


A.     OILS  AND  FATS.     GLYCERIDES. 


CHAPTER  VI. 

VEGETABLE  OILS. 
(1)  Drying  Oils. 

Linseed  Oil. — Percentage  of  oil  in  seeds  38  to  40. 

Preparation. — Linseed  oil  is  prepared  from  the 
seeds  of  the  flax-plant  by  expression  or  extraction. 
The  oil  receives  its  name  according  to  the  locality 
where  the  seed  is  grown.  Calcutta,  La  Plata,  and 
Western  are  some  of  the  brands  in  this  market;  the 
first  being  considered  to  be  the  best,  although  some- 
times equalled  by  the  last. 

Properties. — It  is  of  a  golden-yellow  color  and  high 
specific  gravity,  the  highest  of  any  fatty  oil  likely  to 
be  used  as  an  adulterant.  On  exposure  to  the  air  it  ab- 
sorbs oxygen — often  causing  spontaneous  combustion 
— and  dries  to  a  gummy,  insoluble  substance,  linoxyn. 

Composition. — It  contains  the  glycerides  of  isolino- 
lenic,  linolenic,  linolic,1  oleic,  stearic,  palmitic,  and 

myristic  acids. 

CONSTANTS. 

Sp.  Gr.  15°  C.        Maumeng.  Elaidin.         Iodine.1      Saponification. 

.9315-.9371     103°-126°C.       Liquid       170-193     187.6-195.2 

90°  and  solid.    167.6 

.934.  111°  176  191 

1  Hazura  and  Griissner,  Monatsh.,  9,  180  (1888). 
2 Obtained  by  Hiibl's  method;   this  is  true  of  this  constant 
throughout  the  book. 

103 


104  EXAMINATION  OF  CERTAIN  OILS. 

Adulterants.  —  Corn,  Cotton-seed,  Fish,  and 
Rosin  oils. 

All  these  adulterants  lower  the  constants  given 
and  diminish  its  drying  power;  Cotton-seed  oil 
would  be  shown  by  the  Bechi  test  (page  72) ;  Rosin 
oil  by  the  low  Saponification  Value,  it  being  un- 
saponifiable,  by  the  Liebermann-Storch  reaction 
(page  120),  and  by  the  rotary  power.  Fish  oil, 
usually  menhaden  oil,  p.  132,  may,  if  present  in 
large  quantity,  be  detected  by  its  odor  when  warmed. 
For  the  detection  of  smaller  quantities,  and  par- 
ticularly of  the  deodorized  oil,  resort  must  be  had  to 
the  isolation  of  phytosterol  and  cholesterol  (p.  90). 
These  should  be  converted  into  the  acetates  by 
boiling  with  acetic  anhydride,  recrystallized  from 
absolute  alcohol  four  or  five  times  or  until  a  constant 
melting  point  is  obtained.  Bomer  and  Winter  state 
that  the  melting  point  of  the  phytosterol  acetate 
crystals  from  pure  linseed  oil  is  128°-129°,  and  that 
if  cholesterol  be  present  a  much  lower  melting  point 
is  obtained. 

Uses. — For  preparation  of  paints  and  as  " boiled" 
and  "bleached  oil"  for  preparation  of  varnishes;  by 
treatment  with  sulphur  chloride  for  manufacture  of 
rubber  substitutes;  and  for  soft  soaps. 

"Boiled  Oil." — By  heating  the  oil — preferably  in 
a  steam  jacketed  kettle — from  130°  C.  upward,  with 
or  without  the  addition  of  litharge,  red  lead,  lead 
acetate,  manganese  dioxide  or  borate,  the  oil  becomes 
oxidized,  changes  color,  and  dries  much  more  rapidly. 

The  constants  of  boiled  oil  are  as  follows: 


VEGETABLE  OILS.  105 

CONSTANTS.1 

Sp.  Gr.  15°  C.         Maumen£.         Iodine.  Valenta. 

.936-.93S  100°  C.       164-178        60°-74°  C. 

Bleached  Oil. — This  is  an  oil  prepared,  by  special 
processes  kept  jealously  guarded,  for  the  use  of 
varnish-makers.  It  may  be  prepared  by  heating 
linseed  oil  hotter  than  in  the  preparation  of  "  boiled 
oil, "  to  260°  to  300°  C.,  or  by  forcing  oxygen  through 

the  oil. 

CONSTANTS.1 

Sp.  Gr.  15°  C.          Maumend.  Iodine.  Valenta. 

.032-.934  104°  C.  160  60°  C. 

Mastbaum  2  states  that  pressed  linseed  oil  has  a 
higher  iodine  value  than  extracted  because  the  more 
fluid  portion  is  pressed  out,  and  further,  that  the 
iodine  value  changes  with  the  age  of  the  oil. 

Linseed  oil  for  varnish-making  and  other  refined 
purposes  should  separate  but  a  small  quantity  of 
mucilage  when  heated  to  300°  C.  The  oil  should 
be  very  rapidly  heated  to  this  temperature  in  a 
metal  vessel,  poured  into  a  test-tube,  and  allowed 
to  cool.  A  suitable  oil  shows  little  or  no  deposit, 
whereas  a  bad  one  may  separate  an  amount  equal 
in  volume  to  the  oil  used. 

Hexabromide  Test.  —  This  is  of  great  value  to 
determine  the  purity  of  a  linseed  oil.  If  the  yield 
of  hexabromides  from  a  linseed  oil  is  less  than 
twenty  per  cent.,  foreign  oil  is  present;  fatty  acids 
from  genuine  linseed  oils  yield  usually  from  thirty 

1  Gill  and  Lamb,  J.  Am.  Chem.  Soc.,  21,  29  (1899). 
'Mastbaum,  Z.  angew.  Chem.,  23,  719;    abstr.  J.  Soc.  Chem. 
Ind.,  16,  150  (1897). 


106  EXAMINATION  OF  CERTAIN  OILS. 

to  forty-two  per  cent,  of  bromides.  The  bromides 
of  these  acids  melt  at  175°-180°  to  a  dear  liquid, 
while  those  obtained  from  fish,  liver,  and  blubber 
oils  do  not  melt  even  at  200°  and  change  into  a  dark 
mass.  The  test  is  best  performed  according  to 
the  method  of  Hehner  and  Mitchell : *  One  or  two 
grams  of  the  oil  (0.3  gr.  fatty  acids)  are  dissolved 
in  40  cc.  of  ether  to  which  a  few  cubic  centimeters 
of  acetic  acid  have  been  added.  The  solution  is 
cooled  to  5°  and  bromine  added  drop  by  drop 
(keeping  the  flask  cool)  until  the  color  of  bromine 
persists.  The  mixture  is  allowed  to  stand  three 
hours  to  ensure  complete  absorption  of  the  bromine, 
filtered  through  a  weighed  asbestos  filter,  and  the 
precipitate  washed  successively  with  5  cc.  each  of 
cooled  acetic  acid,  alcohol,  and  ether.  The  precip- 
itate is  dried  in  a  water  oven  to  constant  weight. 
Linseed  oil  yields  from  23  to  38  per  cent,  of  bro- 
mides; poppy,  corn,  cotton-seed,  almond,  olive,  and 
in  some  cases  tung  oil,  yield  none;  walnut  oil  1.5-2.0, 
fish  oil  49.0-52,  Japan  fish  oil  22,  cod-liver  oil  30-43, 
shark-liver  oil  19-22,  seal  oil  27,  whale  oil  15-25. 

Boiled  oils  2  can  be  detected  by  the  lower  percent- 
age of  bromides  obtained  in  this  test;  where  raw 
oil  gives  24  per  cent.,  boiled  oils  give  from  8.4  to  21. 

Chinese  Wood  Oil. — Percentage  of  oil  in  seeds 
35  to  40. 

Preparation.—  This  oil,  called  also  Japanese  Wood 
oil  or  Tung  oil,  is  obtained  from  the  seeds  of  the 

1  Analyst,  23,  313  (1898). 

3  Lewkowitsch,  Analyst,  29,  334  (1904). 


VEGETABLE  OILS  107 

Elceococca  vernicia,  and  must  not  be  mistaken  for 
gurjun  balsam,  also  known  as  wood  oil. 

Properties.  —  It  is  pale  yellow  to  dark  brown,  of 
unpleasant  taste  and  odor.  On  exposure  to  light 
it  is  slowly  changed  to  a  solid  fat,  owing  to  the  con- 
version of  the  elseomargarine  into  its  isomer,  elseo- 
stearine.  It  dries  more  rapidly  than  linseed  oil, 
forming  a  hard  film  of  little  adhesive  power  to  the 
surface  beneath.  It  does  not  dry  on  the  surface  or 
in  layers,  as  does  linseed. 

Composition.  —  It  consists  of  the  glycerides  of  oleic 
and  elaeomargaric  acids.1 

CONSTANTS. 

Sp.  Gr.  15°  C.          Iodine.  Saponification. 

.940  155-165.7  190-197 

When  heated  above  200°  C.  it  gelatinizes  and 
then  neither  melts  nor  dissolves. 

Uses.  —  Wood  oil  cannot  be  regarded  as  a  substi- 
tute for  linseed  oil;  when  mixed  with  it,  it  has  given 
excellent  results,  especially  for  out-of-door  work. 
When  heated  with  driers  at  about  160°  C.  it  has 
been  used  to  good  advantage  in  the  manufacture  of 
oil  varnishes  and  enamel  paints.2  It  is  used  as  a  floor 
varnish,  in  the  manufacture  of  water-proof  materials, 
and  products  resembling  oilcloth. 

Poppy-seed  Oil.  —  Per  cent,  oil  in  seeds  40-50. 

Preparation.  —  Poppy-seed  oil  is  prepared  from  the 
seeds  of  the  common  poppy. 


.  Bull.  Soc.  Chim.,  26,  286  (1901);    Compt.  rend.,  71, 
649;  72,501. 

3Toch,  "  Chemistry  and  Technology  of  Mixed  Paints." 


108  EXAMINATION  OF  CERTAIN  OILS. 

Properties. — The  "cold  drawn"  oil  is  colorless  or 
pale  golden  yellow,  that  of  the  second  pressing  of  a 
reddish  color;  the  taste  is  pleasant,  and  it  is  practi- 
cally odorless.  It  dissolves  in  twenty-five  volumes 
of  cold  or  six  of  boiling  alcohol. 

CONSTANTS. 

Sp.  Gr.  15°  C.  Maumene".  Iodine.  Saponification. 

.924-.9S7  87°  C.  133-143  190-197 

.925  138  193 

Adulterants. — The  chief  adulterant  is  Sesame  oil, 
detected  by  the  lower  Iodine  Value  and  Baudouin 
test. 

Uses. — The  oil  is  used  as  a  salad  oil  and  for  mixing 
and  grinding  artists'  colors. 

Sunflower  Oil. — Percentage  of  oil  in  seeds  30. 

Preparation. — Sunflower  oil  is  obtained  from  the 
seeds  of  the  common  sunflower. 

Properties. — It  is  a  pale  yellow  oil  of  bland  taste 
and  pleasant  odor. 

CONSTANTS. 

Sp.  Gr.  15°  C.  Maumend.  Iodine.  Saponification. 

.924-.92G  67°-75°  C.  118-133  190-194 

Gives  Bechi  but  not  Halphen  or  Baudouin  test. 
Uses. — For  adulterating  other  oils,  as  olive,  as  an 
edible  oil,  for  burning,  soap-  and  varnish-making. 

(2)  Semi-drying  Oils. 

Corn  Oil. — Percentage  of  oil  in  seeds  6  to  10. 
Preparation. — Corn  or  Maize  oil  is  prepared  by 
Expression  from  the  germ  of  the  corn  separated  in 


VEGETABLE  OILS.  109 

the  manufacture  of  starch,1  or  from  the  residues 
from  the  fermentation  of  alcohol.2 

Properties. — The  former  oil  is  pale  to  golden  yel- 
low, the  latter  reddish  brown. 

CONSTANTS. 

Sp.  Gr.  15°  C.  Maumen(?.  Elaidin.         Iodine.  Saponification. 

.9215-.927  56°-88°  C.     Pasty.     111-123  188-193 

.922  85°                               115  191 

.922  100°                             124  188 

Adulterants.  —  Mineral  and  Rosin  oils.  These 
would  be  detected  by  the  lowering  of  the  constants 
(except  Specific  Gravity),  and  the  latter  by  the 
Liebermann-Storch  reaction. 

Composition. — It  contains  the  glycerides  of  pal- 
mitic, arachidic,  oleic,  linoleic  and,  possibly,  stearic 
acids. 

Uses. — For  adulterating  other  oils,  as  linseed, 
lard,4  and  olive,  and  for  painting,  burning,  lubricat- 
ing, and  soap-making,  especially  soft  and  transparent 
soaps. 

Cotton-seed    Oil. — Percentage  of   oil  in  seeds  25. 

Preparation. — Cotton-seed  oil  is  obtained  by  press- 
ing the  seeds  of  the  cotton-plant;  when  first  pressed 
it  is  ruby-red  or  black,  and  is  purified  by  treatment 
with  caustic  soda,  carrying  down  the  gelatinous  sub- 
stances and  color  as  " cotton-seed  foots."  The 

1  J.  Soc.  Chem.  Ind.,  11,  286  (1892). 

2  Kriegner,  Dingier  pol.  J.  (1895),  39  ;  abstr.  J.  Soc.  Chem.  Ind., 
14,  287  (1895). 

3  Boiled  corn  oil. 

4  Its  presence  can  be  told  by  the  presence  of  sitosterol.     See 
articles  by  Gill  and  Tufts,  J.  Am.  Chem.  Soc.,  25,  254  (1903).    Also 
McPherson  and  Ruth,  ibid.,  29,  921  (1907). 


110  EXAMINATION  OF  CERTAIN  OILS. 

grades  in  the  market  are  Summer  White  and  Sum- 
mer Yellow,  and  Winter  White  and  Winter  Yellow, 
according  to  the  temperature  or  season  of  pressing. 

Properties. — It  is  pale  to  deep  yellow  in  color,  and 
absorbs  oxygen  slowly  from  the  air. 

Composition. — It  contains  the  glycerides  of  stearic, 
palmitic,  oleic,  linoleic  acids,  and  some  hydroxy- 
acids  not  yet  investigated.  (Hazura,  Fahrion.) 

CONSTANTS. 

Sp.  Gr.  15*  C.        Maumen£.        Elaidin.         Iodine.        Saponification. 
.9216-.930        70°-90°C.      Pasty.      101-117          191-196 
.922  76°  108 

Adulterants. — It  is  rarely  adulterated.  Linseed 
oil  is  used  for  this  purpose  when  the  price  permits. 

Uses. — For  adulterating  other  oils,  as  a  cooking 
oil  both  by  itself  and  when  mixed  with  suet,  as 
"Cottolene,"  "Cotosuet,"  etc.,  and  for  soap  stock; 
it,  however,  occasions  a  browning  of  the  product. 

Sesame  Oil. — Percentage  of  oil  in  seeds  50  to  57. 

Sesame  oil,  known  also  as  Gingili  or  Teel  oil,  is 
prepared  from  the  seeds  of  the  sesame-plant. 

Properties. — It  is  odorless,  of  a  pale  or  deep  yellow 
color  and  pleasant  taste. 

Composition. — It  contains  the  glycerides  of  stearic, 
palmitic,  oleic,  and  linolic  acids,  also  other  bodies1 
the  composition  of  which  is  not  exactly  known,  to 
which  the  color  reaction  (page  76)  is  probably  due. 


»B6mer,  Chem.  Centralb.,  70,  ii.  729  (1899);  Kreis,  Chem.  Ztg., 
27,  1030,  ibid.,  28,  956  (1904);  Canzoneri  and  Perciabosco,  Gaz. 
Chim.  ital.,  33,  253. 


VEGETABLE  OILS.  Ill 

CONSTANTS. 

6p.  Gr.  15°  C.        Maumend.        Elaidin.         Iodine.        Saponification. 
.022-.924  65°  C.         Pasty.       103-115        187-194 

Adulterants.  —  Cotton-seed,  Peanut,  Rape,  and 
Poppy-seed. 

Cotton-seed  oil  would  be  shown  by  the  Bechi  test, 
Peanut  oil  by  the  low  Specific  Gravity  and  isolation 
of  arachidic  acid;  Rape  oil  would  lower  all  the  con- 
stants and  Poppy-seed  oil  raise  them,  especially  the 
Iodine  (138)  and  Maumene*  (87°)  Values. 

The  Baudouin  test  (page  76)  is  the  characteristic 
test  for  the  presence  of  Sesame  oil. 

Uses. — It  finds  application  as  an  edible  and  burn- 
ing oil,  also  in  tanning  and  soap-making. 

Rape-seed  Oil. — Per  cent,   of  oil  in  seeds  33-43. 

Preparation. — This  oil,  otherwise  known  as  Colza 
oil,  is  obtained  from  the  seeds  of  Brassica  campestris 
or  its  varieties,  colza  or  turnip. 

Properties. — It  is  of  pale  yellow  color,  peculiar 
odor,  and  harsh  taste. 

Composition. — The  glycerides  of  stearic,  oleic, 
erucic,  rapic  and  arachidic1  acids  are  contained  in 
the  oil.2 

The  free  fatty  acids  vary  from  0.5  to  6.2  per  cent. 

CONSTANTS. 

Sp.  Gr.  15°  C.        Maumend.        Elaidin.         Iodine.         Saponification. 
.913-.917          49°-64°  94-106          168-178 

.916  55°  Pasty.        101  174 


1  Archbutt,  J.  Soc.  Chem.  Ind.,  17.  1009  (1898). 
1  Reimer  and  Will,  Ber.,  20,  2388  (1887). 


112  EXAMINATION  OF  CERTAIN  OILS. 

Adulterants.  —  Cotton-seed,  Poppy-seed,  Hemp- 
seed,  Linseed,  and  refined  Fish  oil. 

Cotton-seed  oil  would  be  indicated  by  Maumene 
figure  (76)  and  Bechi  test;  Poppy-seed  oil  by  Iodine 
Value  (138);  Hemp-seed  and  Linseed  by  Specific 
Gravity  (.934)  and  Iodine  Value  (176);  Fish  oil  by 
the  odor  and  high  Iodine  Value. 

Rape-seed  oil  is  distinguished  by  its  almost  com- 
plete insolubility  in  glacial  acetic  acid  (Valenta  test) 
and  by  its  high  viscosity. 

According  to  Palas,1  if  colza  oil  be  agitated  with 
rosaniline  bisulphite,  a  rose-red  coloration  is  ob- 
tained. Other  oils  of  this  and  the  preceding  group 
are  unchanged,  with  the  exception  of  linseed,  which 
is  changed  to  golden  yellow.  The  reagent  is  pre- 
pared by  mixing  together  in  the  cold  thirty  cubic 
centimeters  of  a  one  per  cent,  solution  of  fuchsin, 
twenty  cubic  centimeters  sodium  bisulphite,  1.31 
specific  gravity,  two  hundred  cubic  centimeters  water, 
and  five  cubic  centimeters  of  sulphuric  acid.  The  test 
is  capable  of  detecting  two  per  cent,  of  colza  oil. 

Uses. — It  is  used  as  a  lubricant  and  a  burning  oil; 
because  of  the  difficulty  with  which  it  is  saponified 
it  finds  little  application  in  soap-making. 

Blown  Rape-seed  Oil. — See  under  Blown  Oils, 
page  127. 

Castor  Oil. — Percentage  of  oil  in  seeds  50. 

Preparation. — Castor  oil  is  obtained  from  the  seeds 
of  the  castor-oil  plant. 

1  Analyst,  22,  45;  abstr.  La  Nature  (1897). 


VEGETABLE  OILS.  113 

Properties. — It  is  colorless  or  pale  greenish,  of  mild 
taste  changing  to  harsh,  especially  with  the  Ameri- 
can oils. 

Composition. — It  contains  the  glycerides  of  ricin- 
oleic,  dihydroxystearic,  and  stearic  acids,  and  an 
active  principle  to  which  it  probably  owes  its 
cathartic  properties. 

The  free  fatty  acids  vary  from  0.7  to  14  per  cent. ; 
average  about  1. 

CONSTANTS. 

Sp.  Gr.  15°  C.         Maumend.         Acetyl  Value.         Iodine.         Saponification. 
.959-.96S  47°  C.  150  81-90  176-186 

Adulterants. — Blown  oils,  either  Linseed,  Rape,  or 
Cotton-seed,  and  Rosin  oils. 

These,  though  but  ten  per  cent,  be  present,  cause 
a  turbidity  with  absolute  alcohol,  with  which  castor 
oil  is  miscible  in  every  proportion,  as  it  is  with 
glacial  acetic  acid.  Rosin  oil  would  be  shown  by 
the  lowering  of  the  saponification  value. 

Uses. — Castor  oil  is  employed  in  the  manufacture 
of  Turkey  red  oil,  for  soap-making,  illumination, 
and  in  medicine. 

According  to  Lane  castor  oil  can  be  determined 
in  mixtures,  soaps,  and  Turkey-red  oils  by  making 
use  of  the  fact  that  the  lead  soaps  of  this  oil  are 
wholly  insoluble  in  petroleum  ether  of  boiling  point 
28°-30°  or  38°-40°  C.1 

(3)  Non-Drying  Oils. 
Almond  Oil. — Percentage  of  oil  in  seeds  45  to  55. 


J.  Soc.  Chem.  Ind.,  26,  597  (1907). 


114  EXAMINATION  OF  CERTAIN  OILS. 

Preparation. — Almond  oil  is  obtained  from  the 
seeds  of  two  varieties  of  the  almond-tree,  the  sweet 
and  bitter  almond,  the  latter  yielding  the  more  oil. 

Properties. — It  is  a  bland  thin  oil  of  pale  yellow 
color,  mainly  pure  olein  with  some  linolein. 

CONSTANTS. 

Sp.  Gr.  15°  C.  Maumend.  Elaidin.  Iodine.  Saponification. 

.914-.920  53°  C.  Solid.  93-102  190 

.918  97 

Adulterants. — It  is  adulterated  with  Peach  and 
Apricot  Kernel  oils,  Cotton-seed,  Peanut,  Lard, 
Olive,  Sesame,  and  Poppy-seed  oils. 

The  first  two  are  well-nigh  impossible  of  detection. 
Cotton-seed  oil  would  be  indicated  by  the  Maumene 
figure  (76)  and  Bechi  or  Halphen  test.  Peanut  oil 
would  be  shown  by  the  isolation  of  arachidic  acid. 
Lard  oil  by  the  odor  when  heated  and  by  the  high 
melting  point  of  the  fatty  acid  (35°  C.),  and  also 
Olive  by  the  deposition  of  stearin  when  cooled  to 
— 5°.  Sesame  oil  could  be  detected  by  the  Baudouin 
test  and  Poppy-seed  by  the  Iodine  Value  (138). 

Uses. — Almond  oil  is  used  in  medicine  or  when- 
ever a  fairly  permanent  oil  is  required. 

Peanut  Oil. — Percentage  of  oil  in  seeds  50. 

Preparation. — By  the  cold  pressing  of  the  common 
peanut  a  colorless,  pleasant-tasting  oil  is  obtained, 
which  is  used  as  a  salad  oil;  a  second  pressing 
yields  an  oil  of  inferior  quality,  used  as  an  edible 
and  burning  oil;  a  third  pressing  at  a  higher  tem- 
perature yields  a  grade  employed  in  soap-making. 

Properties. — It  varies  in  color  from  white  to  yellow. 


VEGETABLE  OILS.  115 

Composition. — It  contains  the  glycerides  of  stearic, 
palmitic,  linolic,  oleic,  arachidic,  and  lignoceric 
acids.1 

CONSTANTS. 

Sp.  Gr.  15°  C.  Maumend.  Elaidin.  Iodine.  Saponification. 

.916-.921          45-75°  C.          Solid.          85-105  189-197 

.917  51°  98  194 

Adulterants.  —  Cotton-seed,  Rape,  Sesame,  and 
Poppy-seed  are  used  to  adulterate  this  oil. 

Cotton-seed  oil  would  be  shown  by  the  rise  in  the 
melting  point  of  the  fatty  acids,  those  of  peanut  oil 
melting  at  about  28°,  while  those  from  cotton-seed 
melt  about  ten  degrees  higher;  it  would  further  be 
shown  by  the  Bechi  test.  Rape  oil  would  be  indi- 
cated by  the  low  Saponification  Value  (175),  Sesame 
oil  by  the  Baudouin  test,  and  Poppy-seed  oil  by  the 
Specific  Gravity  (.924)  and  high  Iodine  Value  (138). 

Characteristic  Test. — The  oil  can  be  detected  in 
other  oils  by  the  isolation  of  its  peculiar  acid, — ara- 
chidic acid.  This  is  effected,  according  to  Renard's 2 
process — as  modified  by  Tolman  3 — as  follows : 

Weigh  20  grams  of  oil  into  an  Erlenmeyer  flask. 
Saponify  with  alcoholic  potash,  neutralize  exactly 
with  dilute  acetic  acid,  using  phenolphthalein  as 
indicator,  and  wash  into  a  500  cc.  flask  containing 
a  boiling  mixture  of  100  cc.  of  water  and  120  cc. 
of  a  20  per  cent,  lead  acetate  solution.  Boil  for  a 

^ossmann  and  Scheven,  Ann.,  94,  230  (1885);  Kreiling,  Ber.r 
21,  880  (1888);  Caldwell,  Ann.,  101.  97  (1857). 

'Renard,  Compt.  rend.,  73,  1330  (1871);  also  Archbutt,  J.  Soc. 
Chem.  Ind.,  17,  1124. 

'Bull.  107,  U.  S.  Dept.  Agriculture  (1907),  p.  145, 


116  EXAMINATION  OF  CERTAIN  OILS. 

minute  and  then  cool  the  precipitated  soap  by  im- 
mersing the  flask  in  water,  occasionally  giving  it  a 
whirling  motion  to  cause  the  soap  to  stick  to  the 
sides  of  the  flask.  After  the  flask  has  cooled,  the 
water  and  excess  of  lead  can  be  poured  off  and  the 
soap  washed  with  cold  water  and  with  90  per  cent, 
(by  volume)  alcohol.  Add  200  cc.  of  ether,  cork, 
and  allow  to  stand  for  some  time  until  the  soap  is 
disintegrated;  heat  on  the  water-bath,  using  a 
reflux  condenser,  and  boil  for  about  five  minutes. 
In  the  oils  most  of  the  soap  will  be  dissolved,  while 
in  lards,  which  contain  much  stearin,  part  will  be 
left  undissolved.  Cool  the  ether  solution  of  soap  to 
15°  or  17°  C.  and  let  it  stand  until  all  the  insoluble 
soaps  have  crystallized  out  (about  twelve  hours). 

Filter  and  thoroughly  wash  the  precipitate  with 
ether.  Wash  the  soaps  on  the  filter  back  into  the 
flask  by  means  of  a  stream  of  hot  water  acidified 
with  hydrochloric  acid.  Add  an  excess  of  dilute 
hydrochloric  acid,  partially  fill  the  flask  with  hot 
water,  and  heat  until  fatty  acids  form  a  clear  oily 
layer.  Fill  the  flask  with  hot  water,  allow  the  fatty 
acids  to  harden  and  separate  from  the  precipitated 
lead  chlorid,  wash,  drain,  repeat  washing  with  hot 
water,  and  dissolve  the  fatty  acids  in  100  cc.  of 
boiling  90  per  cent,  (by  volume)  alcohol.  Cool  to 
15°  C.,  shaking  thoroughly  to  aid  crystallization. 

From  5  to  10  per  cent,  of  peanut  oil  can  be  detected 
by  this  method,  as  it  effects  a  complete  separation  of 
the  soluble  acids  from  the  insoluble,  which  interfere 
with  the  crystallization  of  the  arachidic  acid.  Filter, 


VEGETABLE  OILS.  117 

wash  the  precipitate  twice  with  10  cc.  of  90  per  cent, 
(by  volume)  alcohol,  and  then  with  alcohol  70  per 
cent,  by  volume.  Dissolve  off  the  filter  with  boiling 
absolute  alcohol,  evaporate  to  dryness  in  a  weighed 
dish,  dry  and  weigh.  Add  to  this  weight  0.0025 
gram  for  each  10  cc.  of  90  per  cent,  alcohol  used  in 
the  crystallization  and  washing  if  done  at  15°  C. ;  if 
done  at  20°  add  0.0045  gram  for  each  10  cc.  The 
melting  point  of  arachidic  acid  thus  obtained  is 
between  71°  and  72°  C.  Twenty  times  the  weight 
of  arachidic  acid  will  give  the  approximate  amount 
of  peanut  oil  present.  No  examination  for  adulter- 
ants in  olive  oil  is  complete  without  making  the  test 
for  peanut  oil.  Arachidic  acid  has  a  characteristic 
structure  and  can  be  detected  by  the  microscope. 

Uses. — These  have  been  already  given  under  the 
preparation. 

Olive  Oil.— Percentage  of  oil  in  the  fruit  40  to  60. 

Preparation. — Olive  oil  is  prepared  by  expressing 
or  extracting  the  fruit  of  the  olive-tree;  the  oil 
varies  greatly  according  to  the  tree,  there  being  no 
less  than  three  hundred  varieties  in  Italy  alone,  and 
also  the  degree  of  ripeness  and  manner  of  gathering 
of  the  fruit  itself. 

Properties. — It  varies  in  color  from  almost  color- 
less to  golden  yellow  or  green. 

Composition. — It  contains  palmitin,  stearin,  olein, 
and  linolin,1  the  solid  glycerides  constituting  about 
twenty-eight  per  cent,  of  the  oil. 

1  Ilazura  and  Griissner. 


118  EXAMINATION  OF  CERTAIN  OILS. 

The  free  fatty  acids  vary  from  1  to  24  per  cent. 

According  to  Allen,  an  oil  containing  more  than 
five  per  cent,  of  free  fatty  acids  is  unfit  for  a  lubri- 
cant, as  it  attacks  the  metals,  and  also,  according  to 
Archbutt,  as  a  burning  oil,  as  it  causes  charring  of 
the  wick. 

CONSTANTS. 

Sp.  Gr.  15°  C.  Maumend.  Elaidin.  Iodine.  Saponification. 

.914-.918  41°-47°C.     Very  solid.    78.2-91.5  185-203 

.916  35°  82  190 

Adulterants. — Cotton-seed,  Peanut,  Rape,  Sesame, 
Poppy-seed,  and  Lard. 

Cotton-seed  oil  would  be  shown  by  the  Bechi  test 
and  the  high  Maumen£  figure  (76)  and  Iodine  Value 
(108).  Peanut  oil  by  isolation  of  Arachidic  Acid  and 
high  Iodine  Value  (98).  Rape  oil  would  be  indi- 
cated by  the  Saponification  Value  (175)  and  Iodine 
Value  (101).  Sesame  oil  by  the  Baudouin  test. 
Poppy-seed  oil  by  the  Iodine  Value  (138)  and  Mau- 
men6  figure  (87). 

Olive  oil  is  characterized  by  the  low  Maumene* 
and  Iodine  Values  and  by  the  solid  elaidin. 

Uses. — It  is  used  as  an  edible  oil,  for  oiling  tex- 
tiles, as  a  soap  stock,  and  as  a  burning  oil. 


ROSIN    OILS    AND   TURPENTINE. 

Rosin  Oil. — Rosin  oil  is  prepared  by  the  distilla- 
tion of  common  rosin  (colophony)  in  stills  holding 
about  thirty  barrels.  About  eighty-five  per  cent,  of 
rosin  oil  and  three  per  cent,  of  rosin  spirits,  or  pino- 


VEGETABLE  OILS.  119 

line,  are  obtained.  Acid  water,  gas,  coke,  and  losses 
account  for  the  remaining  twelve  per  cent.  The 
product  obtained  is  a  thick  oil,  known  as  "First 
Run;"  this  is  redistilled,  yielding  a  darker-colored 
oil,  called  "Second  Run."  This  operation  is  re- 
peated, yielding  "Third,"  "  Fourth,"  and  even  "  Fifth 
Run." 

The  oil  in  the  market  is,  however,1  in  nearly  every 
case  the  product  of  a  single  distillation;  upon  dis- 
tilling five  to  six  thousand  pounds  of  rosin  the  fol- 
owing  yields  are  obtained. 

Water  0.5  to    1  per  cent. 

Naphtha  1.5  to    2  per  cent. 

Raw  oil]  84     to  88  per  cent. 

Pitch  3     to    5  per  cent. 

Gases,  loss,  etc.  6     to    8  per  cent. 

CONSTANTS. 

Sp.  Gr.  Iodine.  Free  Acid. 

975-.995          112-115     .05-4.8  per  cent. 

PROPERTIES  OF  ROSIN  OILS. 

ROSIN   OIL,    SECOND   RUN. 

Sp.  Gr.  at  15°.        Maumene".         Iodine.        Saponification. 

.987  32  59  34 

Free  acid,  12.6. 

ROSIN  OIL,  THIRD  RUN. 

Sp.  Gr.  at  15°.         Maumene".         Iodine.         Saponification. 

.985  34.0  77  25 

Free  acid,  13.7. 

ROSIN  OIL,  FOURTH  RUN. 

Sp.  Gr.  at  15°.        Maumene*.         Iodine.        Saponification. 

.981  32.5  23  20 

Free  acid,  9.6. 

1  Spayd,  Chem.  Eng'r,  3,  218  (1905). 


120  EXAMINATION  OF  CERTAIN  OILS. 

Deodorized  Rosin  oil  is  that  portion  of  the  later 
runs  which  is  freed  from  the  " spirits"  by  fractional 
distillation. 

Uses. — " First  Run"  is  employed  in  making  axle 
grease,  in  oiling  leather,  and  making  cements. 
" Second  Run"  finds  use  in  printing  ink  and  in  the 
leather  industry.  " Third"  and  "Fourth"  runs  are 
used  mainly  for  mixing  with  other  oils. 

Qualitative  Test. — Rosin  oil  may  be  detected  by 
the  Liebermann-Storch  reaction.1  One  to  two  cubic 
centimeters  of  the  oil  are  shaken  with  an  equal  quan- 
tity of  acetic  anhydride  and  gently  warmed.  When 
cool,  the  acetic  anhydride  is  pipetted  off  and  tested 
by  the  addition  of  one  drop  of  concentrated  sulphuric 
acid.  A  fine  violet  color  is  produced  in  the  presence 
of  rosin  oil.  Cholesterol  which  is  contained  in  the 
animal  fats  produces  a  similar  coloration;  this  can 
be  removed  by  saponifying  the  oil  as  completely  as 
possible  and  shaking  out  the  somewhat  dilute  soap 
solution  with  ether  or  petroleum  ether.  The  soap 
solution  is  then  acidified,  setting  free  the  fatty  acids, 
and  these  treated  with  acetic  anhydride  as  if  they 
were  the  oil. 

Renard's  test  modified  by  Allen  2  consists  in  add- 
ing a  few  drops  of  stannic  bromide,  dissolved  in 
carbon  bisulphide,  to  a  few  drops  of  the  oil,  also 
dissolved  in  carbon  bisulphide.  Should  rosin  oil  be 
present  a  violet  color  will  be  produced,  which  on 


1  Storch,  J.  Soc.  Chem.  Ind.,  7,  136  (1888). 
'Commercial  Organic  Analysis,  ii.  463. 


VEGETABLE  OILS.  121 

standing  forms  a  deposit  at  the  bottom  of  the  tube. 
Glacial  acetic  acid  is  recommended  as  a  solvent  in 
the  case  of  mineral  oils,  these  not  dissolving  it  to  any 
appreciable  extent  and  not  masking  the  reaction. 

Wiederhold  l  states  that  rosin  oils  are  dissolved  at 
15°  C.  by  half  their  volume  of  anhydrous  acetone, 
while  mineral  oils,  especially  American,  are  almost 
unacted  upon  by  it. 

Rosin  Spirits. — Its  preparation  has  already  been 
given  under  rosin  oils. 

Properties  and  Composition. — It  has  a  peculiar 
odor  and  contains  heptine,2  C7H12,  which  boils  at 
103-104°  C.  and  absorbs  oxygen  readily. 

CONSTANTS. 

Sp.  Gr.  15°  C.  Maumend.  Iodine. 

.856-.8S3  91°  C.  185 

The  boiling  point  varies  frorh  80°  to  250°  C.  The 
free  acid  is  sometimes  15  per  cent. 

Valenta  3  states  that  rosin  spirits,  or  "  essence  of 
turpentine"  as  he  calls  it,  can  be  distinguished  by 
the  following  reactions:  (1)  acetic  anhydride  and 
one  drop  of  sulphuric  acid  give  an  intense  green 
color;  (2)  one  part  of  oil  and  1  to  2  parts  of  a  6  per 
cent,  solution  of  iodine  in  chloroform  or  carbon 
tetrachloride,  warmed  gently  on  a  water-bath,  give 
intense  green  to  olive-green  colors.  The  strongest 
colors  are  given  by  the  lower  boiling  fractions. 


1  Z.  anal.  Chem.,  33,  111  (1894). 

1  Veitch,  Bureau  of  Chemistry  Circular  No.  36,  p.  31  (1907). 

3  Chem.  Zeit.,  29,  807  (1905);  abstr.  Analyst,  30,  342. 


122  EXAMINATION  OF  CERTAIN  OILS. 

This  last  reaction  is  not  given  by  oil  of  turpentine 
(gum),  pine  resin  oils  (wood  turpentine),  light  petro- 
leum, oil  of  camphor,  or  rosin  oil. 

Adulterants. — Petroleum  and  shale  products. 

Uses. — As  a  substitute  for  gum  turpentine. 

Turpentine.  —  Preparation.  —  Turpentine  is  pre- 
pared1 by  distilling  pine  resin  in  copper  stills  of 
about  eight  hundred  gallons'  capacity;  the  process 
requires  some  care  to  prevent  overheating  and  obtain 
a  fine  quality  of  rosin.  To  aid  the  process,  after  the 
crude  resin  is  melted,  a  stream  of  tepid  water  from 
the  condenser  is  run  into  the  still,  thus  making  a 
distillation  with  steam.  The  yield  and  quality  vary 
according  to  the  length  of  time  the  trees  have  been 
producing  resin,  both  growing  inferior  with  age. 
The  crude  resin,  or  "dippings,"  of  the  first  season  is 
called  "virgin  dip,"  and  produces  the  finest  quality 
of  rosin,  W.  W.  (water  white)  and  W.  G.  (window 
glass);  the  better  grades  are  N,  M,  and  K,  passing 
through  the  poorer  grades  to  the  black  A.  From 
two  hundred  and  twenty-five  barrels  of  soft  turpen- 
tine and  one  hundred  and  twenty  barrels  of  hard 
gum,  the  product  of  a  second  season,  nineteen  hun- 
dred gallons  of  turpentine  and  two  hundred  barrels 
of  amber  rosin,  I,  H,  or  G,  were  produced. 

The  resin  is  chiefly  obtained  from  the  Long-leaf 
Pine,  Pinus  palustris  or  australiSj  known  also  as 
Southern,  Yellow,  or  Hard  Pine. 

1  Condensed  from  a  monograph  on  "  The  Timber  Pines  of  the 
Southern  United  States,"  by  Filibert  Roth,  U.  S.  Dept.  of  Agri- 
culture (1896). 


VEGETABLE  OILS.  123 

Properties  and  Composition.  —  Turpentine  is  a 
colorless  liquid  of  peculiar  taste  and  odor.  On 
exposure  to  the  air  it  absorbs  oxygen  and  gradually 
becomes  resinous.  It  consists  mainly  of  a  hydro- 
carbon, Pinene,  C10H16. 

CONSTANTS. 
Sp.  Gr.  15°  C.  Iodine. 

.8G2-.87  331,1  384-391 3 

The  boiling  point  is  155°  to  156°  C.,  and  eighty- 
five  per  cent,  should  pass  over  between  155°  and 
163°,  the  remainder  below  1830.3  The  flash  point 
is  83°  to  95°  F.  by  the  New  York  State  Board  of 
Health  tester.  American  turpentine  deflects  polar- 
ized light  to  the  right,  although  a  sample  obtained 
from  spruce-trees  had  a  specific  rotation  of  — 40.79.4 

Adulterants.—  Petroleum  and  Shale  Products, 
Rosin  Spirits,  Wood,5  and  Russian  Turpentine  are 
the  chief  adulterations. 

Petroleum  and  Shale  Products:  the  lighter  ones 
would  be  indicated  by  the  lowering  of  the  specific 
gravity,  flash  test,  and  iodine  value,  they  having  a 
value  of  30  and  70  respectively,  and  by  distillation. 
Kerosene  might  be  detected  by  the  "bloom."  To 
determine  the  quantity  of  petroleum  or  heavy  oil 
added,  Vulpius6  floats  a  gram  of  the  suspected 

1  Wilson,  Chem.  Trade  J.,  6,  316 ;  J.  Soc.  Chem.  Ind.,  9,  657 
(1890). 

'Worstall,  ibid.,  23,   302  (1904). 

•Long,  ibid.,  10,  261;  J.  Soc.  Chem.  Ind.,  11,  549.  (1892). 

4  Long,  J.  Am.  Chem.  Soc.,  16,  884  (1894). 

8McCandless,  ibid.,  26,  981  (1904). 

•  Apoth.  Ztg.,  6,  289 ;  abstr.  J.  Soc.  Chem.  Ind.,  10,  800  (1891). 


124  EXAMINATION  OF  CERTAIN  OILS. 

sample  and  of  a  pure  sample  each  in  a  separate 
watch-glass  upon  a  beaker  of  water  kept  at  80°. 
When  the  pure  sample  has  evaporated,  both  are 
weighed,  the  residue  from  the  pure  sample  deducted 
from  the  other,  and  this  difference  represents  the 
heavy  oil  added.  According  to  Burton,1  the  oxida- 
tion with  fuming  nitric  acid  gives  fairly  quantitative 
results  on  the  percentage  of  petroleum  products 
present.  This  is  effected  by  dropping  slowly  one 
hundred  cubic  centimeters  of  the  sample  into  three 
hundred  cubic  centimeters  of  fuming  nitric  acid 
in  a  flask  immersed'  in  cold  water;  the  oxidation 
products  are  dissolved  in  hot  water  and  the  petro- 
leum remains. 

Rosin  Spirits  could  be  detected  by  distillation 
and  treatment  of  the  residue  with  stannic  bromide 
(Renard's  test,  p.  120)  dissolved  in  carbon  bisul- 
phide and  also  Valenta's  test,  p.  50.  The  addition 
of  rosin  spirits  or  wood  turpentine  is  readily  shown 
by  Herzfeld's  test,  the  production  of  a  yellow  color 
by  shaking  with  a  solution  of  sulphurous  acid. 
They  would  also  cause  a  lowering  of  the  iodine 
value,  that  for  rosin  spirits  being  185  *  and  refined 
wood  turpentine  212.2 

McCandless3  claims  to  detect  the  latter  by  distil- 
ling the  turpentine  according  to  Engler's  method 
for  kerosene,  p.  20,  and  determining  the  refraction 
index  of  various  distillates.  "The  flame  used  must 

1Am.  Chem.  J.,  12,  102. 
'Worstall,  loc.  cit. 
3  Loc.  cit. 


VEGETABLE  OILS.  125 

be  small,  the  thermometer  rise  very  slowly,  and 
the  first  half  cubic  centimeter  of  the  distillate 
collected  by  itself,  the  refractive  index  being  taken 
at  25°  C.  In  case  of  no  genuine  oil  will  this  fall 
below  1.4659,  being  usually  1.4665  to  1.4678.  Sev- 
eral samples  of  wood  turpentine  show  readings 
as  low  as  1.4652,  1.4646,  or  even  1.4639.  When 
the  wood  turpentines  do  not  show  a  low  initial 
reading,  they  nearly  always  show  a  high  reading 
on  the  final  portion  of  the  distillate.  I  have  adopted 
the  97th  and  98th  cc.  as  being  in  practice  the 
most  convenient  to  collect  separately  for  the 
purpose  of  making  the  final  refractive  index.  In 
the  case  of  the  genuine  (gum)  spirits  this  reading 
will  not  exceed  1.4765,  usually  much  less,  but 
with  wood  turpentine  will  exceed  1.4765  and  may 
even  reach  1.4840.  A  further  distinction  between 
genuine  and  wood  turpentine  may  be  observed 
during  this  distillation;  in  nearly  all  genuine 
spirits  95  per  cent,  will  have  distilled  over  by  the 
time  the  temperature  reaches  165°  C.,  whereas  with 
wood  turpentine,  when  95  per  cent,  have  come 
over,  the  thermometer  is  much  higher  than  165 °." 

Paul1  says  the  above  method  is  fairly  satisfactory. 

Besides  this  method  Geer2  recommends  the  frac- 
tional distillation  with  steam. 

Russian  Turpentine  would  be  shown  by  the  higher 
temperature  of  distillation,  170°  to  180°.  Pure  tur- 

1  J.  Ind.  and  Eng.  Chem.  1,  27  (1909). 

2  U.  S.  Dept.  Agriculture  Forest  Service  Circular  153  (1908). 


126  EXAMINATION  OF  CERTAIN  OILS. 

pentine  should  leave  no  residue  upon  writing-paper 
after  half  an  hour. 

Uses. — Turpentine  finds  extended  use  as  a  sol- 
vent for  fats,  waxes,  resins,  and  rubber,  and  as  a 
"drier"  in  paints. 

Wood  Turpentine.  — Wood  Spirits,  Stump  Ter- 
pentine. — As  its  name  denotes,  this  is  obtained 
by  distilling  pine  wood  (" light  wood,"  stumps, 
knots,  etc.)  with  steam:  superheated  steam  was 
formerly  employed,  but  modern  practice  uses  direct 
steam,  postponing  destructive  distillation  or  any 
other  process  until  the  spirits  are  first  removed. 
The  wood  is  chipped  as  for  the  manufacture  of 
wood  pulp,  filled  into  horizontal  or  vertical  retorts, 
and  steam  blown  into  them:  this  requires  from 
one  to  twelve  hours  and  the  yield  is  from  6  to  25 
gallons  per  cord,  the  average  being  12  to  15  gallons. 
When  the  stills  are  properly  operated  and  the 
product  is  suitably  refined,  there  should  be  prac- 
tically no  difference  between  the  turpentine  pre- 
pared in  this  way  and  the  ordinary  (gum)  tur- 
pentine.1 

Properties. — It  has  a  specific  gravity  of  0.860  to 
.880  at  20°  C.,  and  95  per  cent,  should  distil  between 
150°  and  185°  C.2  and  an  iodine  number  of  212  to 
352.3 

Adulterants  and  Uses. — The  same  as  for  gum 
turpentine,  which  see.  On  account  of  the  odor  of 


1  Teeple,  J.  Soc.  Chem.  Ind.,  26,  811  (1907). 
'Veitch,  loc.  cit.,  p.  29.  3  McCandless,  loc.  cit. 


VEGETABLE  OILS.  127 

some  varieties  it  is  better  used  for  out-door  paint- 
ing than  for  inside  work. 

Varieties  of  Turpentine  and  Sources. — American 
turpentine,  from  Pinus  palustris  or  australis,  the 
Longleaf  Pine,  dextrorotary. 

English  turpentine,  from  gum  collected  in  Amer- 
ica, from  P.  australis  and  P.  tceda,  Loblolly. 

French,  from  Pinus  maritima,  Sea-pine,  and 
P.  glabra,  Spruce  Pine,  laevorotary. 

German,  from  P.  sylvestris,  Scotch  Pine  or  Fir, 
P.  nigra,  Black  Pine,  and  P.  rotundata. 

Venice,  from  Larix  europcea,   Larch. 

Russian,  from  P.  sylvestris,  and  P.  ledebourii, 
dextrorotary. 

Blown  Oils. — Preparation. — Blown,  Base,  Thick- 
ened, or  Oxidized  oil  is  usually  prepared  by  heat- 
ing the  oil  to  70°  or  110°  in  a  jacketed  kettle  and 
forcing  a  current  of  air  through  it;  after  the  action 
is  once  started  no  further  heating  is  usually  necessary. 

Properties. — The  color  of  the  oil  darkens  slightly 
and  the  density  and  viscosity  are  much  increased. 
Benedikt  and  Ulzer  think  that  the  fatty  acids  are 
oxidized  to  hydroxyacids.  The  oils  submitted  to  this 
process  are  chiefly  Rape  and  Cotton-seed,  although 
it  is  often  applied  to  Linseed,  Sperm,  and  Seal  oils. 


CONSTANTS.1 

Sp.  Gr.  15°  C. 
.967 
.974 

Maumend.  2 
253-(57°) 
227 

Iodine. 
63.6 
56.4 

Saponification. 
197.7  Rape. 
213.3  Cotton-seed. 

.980 

... 

90.7 

208.6  Maize. 

1  Thomson  and  Ballantyne,  J.  Soc.  Chem.  Ind.,  1 1,  506  (1892). 
3  Specific  temperature  reaction. 


128  EXAMINATION  OF  CERTAIN  OILS. 

Uses. — On  account  of  their  high  viscosity,  blown 
oils  are  used  to  mix  with  other  oils  for  lubricating 
purposes. 

Palm  Oil. — Preparation. — Palm  oil  is  obtained 
from  the  flesh  or  pericarp  of  the  palm-nut;  this 
grows  in  immense  quantities  on  the  west  coast  of 
Africa.  The  fruits  are  fermented,  whereby  the  oil 
rises  to  the  top,  or  it  is  expressed  from  the  fresh 
fruit.  The  latter  process  yields  the  finer  and  more 
fluid  product. 

Properties. — Owing  to  its  method  of  preparation 
its  properties  are  quite  varied.  It  is  of  a  buttery 
or  tallowy  consistency,  of  orange-yellow  to  dirty 
red  in  color,  and  has  an  odor  in  some  samples 
recalling  that  of  violets.  By  heating  to  a  high 
temperature  or  treatment  with  acids  it  may  be 
bleached. 

Composition. — It  is  mainly  palmitin,  with  some 
olein  and  free  palmitic  acid. 

CONSTANTS. 

Sp.  Gr.  99°  C.  Iodine.  Saponification. 

.859  53-56  196-202 

Adulterants. — Water   and   dirt,    mostly   sand. 

Characteristic  Tests.1  —  Dissolve  100  cc.  of  the 
oil  in  300  cc.  petroleum  ether  and  shake  with 
50  cc.  0.5  per  cent,  potassium  hydrate.  The 
aqueous  layer  is  drawn  off,  acidified  with  hydro- 
chloric acid,  and  shaken  with  10  cc.  carbon  tetra- 
chloride:  a  portion  of  this  solution  is  treated  in  a 

1  Crampton  and  Simons,  J.  Am.  Chem.  Soc.,  27,  272  (1905). 


VEGETABLE  OILS.  129 

porcelain  crucible  with  2  cc.  of  a  mixture  of  one 
part  crystallized  phenol  with  two  parts  carbon 
tetrachloride.  Five  drops  hydrobromic  acid  (sp.  gr. 
1.19)  are  added  and  the  contents  mixed  by  gently 
agitating  the  crucibles.  The  almost  immediate 
development  of  a  bluish-green  color  is  indicative 
of  palm  oil. 

Ten  cubic  centimeters  of  the  oil  are  shaken  with 
an  equal  volume  of  acetic  anhydride,  then  one  drop 
sulphuric  acid  (sp.  gr.  1.53)  is  added  and  the  mixture 
shaken  a  few  seconds.  If  palm  oil  be  present  the 
lower  layers  on  settling  out  will  be  found  to  be 
colored  blue  with  a  tint  of  green.1 

Uses. — For  the  manufacture  of  soap  and  candles 
and  coloring  other  oils. 

Cocoanut  Oil. — Preparation. — Cokernut  oil  is  ob- 
tained from  the  fat  of  the  cocoanut,  the  fruit  of  a 
species  of  palm.  The  finest  quality  is  that  prepared 
in  Cochin  (Malabar)  from  the  fresh  fruit.  Infe- 
rior varieties  are  made  from  the  dried  kernels, 
or  "coprah,"  which  contain  60  to  70  per  cent, 
of  oil. 

Properties. — It  is  a  solid  white  fat  of  bland  taste 
and  peculiar  odor,  readily  turning  rancid.  It  is 
soluble  in  two  volumes  of  absolute  alcohol  at  31°  C. 

Composition. — It  contains  a  larger  proportion  of 
volatile  acids  than  most  oils;  the  glycerides  of 
caproic,  caprylic,  capric,  oleic,  lauric,  and  myristic 
acids  are  among  those  present. 

1  This  test  would  seem  open  to  question. 


130  EXAMINATION  OF  CERTAIN  OILS. 

CONSTANTS. 

Sp.  Gr.  99°  C.  Iodine.  Saponification. 

.874  8-10  253-268 

Adulterants. — It  is  rarely  adulterated. 

Characteristic  Test. — Hanus1  has  devised  a  method 
for  the  detection  of  this  fat  in  other  fats  and  oils 
based  upon  the  volatility  of  the  ethyl  esters  made 
from  the  acid  in  cokernut  oil,  the  "  ethyl  ester  num- 
ber." The  procedure  is  as  follows:  five  grams  of 
the  melted  fat  are  weighed  into  a  200  cc.  Erlen- 
meyer  flask,  and  heated  for  fifteen  minutes  in  an 
oven  at  50°  C.;  exactly  30  cc.  of  -^  alcoholic  potas- 
sium hydroxide  solution  are  then  added  from  a 
burette,  and  the  mixture  is  thoroughly  shaken 
until  perfectly  clear,  usually  about  two  minutes. 
After  keeping  the  contents  of  the  flask  at  a  tem- 
perature of  50°  C.  for  eight  minutes,  2  cc.  of  dilute 
sulphuric  acid  are  added,  the  acid  being  of  such 
concentration  that  the  2  cc.  will  exactly  neutralize 
the  30  cc.  of  potassium  hydroxide  solution.  The 
contents  of  the  flask  are  now  diluted  to  a  volume 
of  145  cc.  with  water,  a  few  pieces  of  quenched 
pumice  are  added,  and  the  mixture  is  distilled, 
using  a  fusible  metal  bath  and  single  bulb  tower. 
The  first  30  cc.  of  alcoholic  distillate  which  comes 
over  is  collected  in  a  graduated  cylinder,  the  next 
100  cc.  of  distillate  being  received  separately  in 
a  100  cc.  flask.  The  whole  distillation  must  not 
take  longer  than  twenty-five  minutes.  Both  frac- 

1  Hanus,  Z.  Nahr.  und  Genussm.,  13,  18  (1907),  16,  577  (1908). 


VEGETABLE  OILS.  131 

tions  of  the  distillate  are  now  transferred  to  two 
separate  flasks;  alcohol  is  added  to  the  aqueous 
distillate  until  a  clear  solution  is  obtained,  the 
free  acidity  of  both  portions  is  neutralized,  using 
phenolphthalein  as  an  indicator,  and  they  are  then 
boiled  with  40  cc.  of  §  alcoholic  potassium  hydrox- 
ide solution.  After  titrating  back  the  excess  of 
alkali,  the  number  of  cc.  of  •&  alkali  required  for 
the  saponification  of  the  esters  from  5  grams  of  the 
fat  is  calculated  from  the  f  used. 

For  cokernut  oil  the  number  of  cubic  centimeters 
of  ^  alkali  required  for  the  saponification  of  the 
esters  in  the  alcoholic  portion  is  from  38  to  44, 
butter  8-9.4,  lard  1.6.  Palm  oil,  23.1.  Cocoa  butter 
1.3-1.6. 

Uses.—  It  is  used  in  soap-making  (marine  soaps), 
in  candle-making,  and  as  an  edible  fat. 


CHAPTER  VII. 

ANIMAL   OILS. 
(1)  Marine  Animal  Oils. 

a.    Fish    Oils. 

Menhaden  Oil. — This  oil  is  otherwise  known  as 
mossbunker,  pogy,  porgy,  or  whitefish  oil. 

Preparation. —  It  is  prepared  from  the  menhaden 
by  steaming  and  expression.  There  are  several 
grades  in  the  market,  differing  in  appearance  ac- 
cording to  the  source  from  which  they  are  derived. 
They  are  Select  Light  Strained,  Select  Light,  Choice 
Brown,  Dark,  and  Gurry  oil.  The  better  varieties  are 
obtained  by  gentle  pressure  and  subsequent  bleach- 
ing, and  the  others  by  the  pressing  of  the  residues. 

Properties. — It  is  yellow  to  brown  in  color,  and 
oxidizes  readily  on  exposure  to  the  air. 

It  is  to  be  noted,  however,  that  the  firm,  hard 
coating  or  "skin"  which  is  formed  on  drying  is 
usually  not  as  closely  adherent  to  the  surface  be- 
neath it  as  that  formed  with  linseed  oil. 

Composition. —  It  apparently  contains  the  glycer- 
ides  of  linoleic,  myristic,  asellic,  and  acetic  acids,  and 
also  isocholesterol. 

CONSTANTS. 
8p.  Gr.  15°  C.  Maumend.  Elaidin.  Iodine.       Saponification. 

.927-.93S         123°-128°C.        Liquid.         139-172         189-192 
.930  126°  154  190 

132 


ANIMAL  OILS.  133 

Adulterants.  —  The  chief  adulterant  is  Mineral 
oil,  which  would  be  shown  by  a  lowering  of  all 
these  constants. 

Uses. — It  is  used  in  currying,  for  adulterating 
other  oils,  as  linseed,  whale,  and  sardine,  as  a  sub- 
stitute for  linseed  oil,  and  as  a  burning  oil  for  mines. 

REFERENCE. 

G.  B.  GOODE,  "  The  Natural  and  Economic  History  of  the  Ameri- 
can Menhaden,"  U.  S.  Commission  of  Fish  and  Fisheries,  vol.  v., 
1879. 

/?.  Liver  Oils. 

Cod  Oil. — Three  varieties  of  cod  or  cod-liver  oil 
are  obtainable  in  the  market,  the  pale  yellow,  or 
" steam  rendered,"  and  the  light  brown,  both  of 
which  are  used  in  pharmacy,  and  for  the  examina- 
tion of  which  recourse  must  be  had  to  larger  works. 
The  other,  the  brown  oil  or  "cod  oil,'7  used  in  curry- 
ing, may  be  derived  from  the  liver  of  any  fish,  hence 
it  is  impossible  to  give  any  data  upon  which  judg- 
ment may  be  formed. 

T.  Blubber  Oils. 

Whale  Oil. — Preparation. — Whale  or  Train  oil 
is  obtained  by  rendering  the  blubber  of  various 
species  of  whales  except  the  sperm  and  bottlenose. 

Properties  and  Composition. — It  has  a  strong 
fishy  odor,  a  "nutty"  taste,  and  is  of  a  light-yellow 
to  yellowish-brown  color.  Little  is  known  regard- 
ing its  constitution.  As  may  be  expected,  its  com- 
position varies  widely. 


134  EXAMINATION  OF  CERTAIN  OILS. 

CONSTANTS. 

Sp.Gr.  15°  C.  Maumene".  Iodine.  Saponification. 

.917-.930  85°-91°C.  110-136  188-193 

.927  88°  120  190 

Adulterant. — It  is  largely  adulterated  with  Seal 
oil,  which  there  is  little  chance  of  detecting. 

Uses. — Whale  oil  is  used  as  a  leather  dressing, 
as  a  burning  oil,  and  to  mix  with  other  oils  as  a 
lubricant. 

(2)  Terrestrial  Animal  Oils. 

Neat's-foot  Oil — Preparation. — Neat's-foot  oil  is 
obtained  from  the  feet  of  neat  cattle.  The  hoofs 
are  separated,  the  bones  of  the  foot  disjointed,  and 
the  latter  boiled  with  water,  the  emulsion  allowed 
to  settle,  and  the  oil  which  rises  separated.  As  is 
the  case  with  all  oils,  that  which  is  obtained  by  the 
least  degree  of  heat  or  pressure  is  the  best. 

Properties. — It  is  of  a  light-yellow  color,  bland 
taste,  possesses  a  peculiar  odor,  and  little  tendency 
to  turn  rancid. 

Composition. — It  is  nearly  pure  olein,  containing 
a  small  quantity  of  stearin,  which  it  frequently 
deposits.  The  free  fatty  acids  may  amount  to  six 

per  cent. 

CONSTANTS. 

Sp.  Gr.  15°  C.          Maumene*.  Elaidin.  Iodine.     Saponification. 

.914-.916        42-49.5°  C.        Solid  at  times.     66-76         194-199 

If  the  iodine  number  be  less  than  63,  it  probably 
contains  hide  oil.  The  fatty  acid  should  be  less  than 
one  per  cent.  Titer  test  may  be  from  17°  to  26°. 

Adulterants.  • —  Fish,  Poppy-seed,  Rape,  Cotton- 
seed, Mineral  oils,  and  other  hoof  oils. 


ANIMAL  OILS.  135 

Fish  oil  would  be  shown  by  the  Iodine  Value 
and  Maumene  test,  also  by  the  odor  when  heated; 
Poppy-seed  oil  by  the  Gravity  (.925)  and  Iodine 
Value  (138);  Rape  oil  by  Saponification  (175)  and 
Iodine  Value  (101);  Cotton-seed  by  the  Bechi  test 
and  Iodine  Value  (108);  Mineral  oil  by  the  lower- 
ing of  all  the  constants  given. 

Uses. — Neat's-foot  oil  finds  application  as  a  lubri- 
cant, either  by  itself  or  mixed  with  other  oils,  and 
for  currying  purposes. 

Horse  Oil — Horse  oil  is  prepared  by  rendering 
dead  horses. 

CONSTANTS. 
Sp.  Gr.  15°  C.  Maumend.  Iodine.  Saponification. 

.916-.922  46°-55°C.  75-86  197.1 

It  is  used  for  mixing  with  and  adulterating  other 
oils,  as,  for  example,  neat's-foot;  when  refined  it 
has  been  used  to  adulterate  olive  oil. 

Lard  Oil.  —  Preparation.  —  Lard  oil  is  obtained 
by  pressing  lard;  upright  screw-presses  are  used 
and  a  pressure  of  about  eight  thousand  pounds  to 
the  square  inch  employed;  from  forty  to  sixty  per 
cent,  of  the  lard  is  obtained  as  oil. 

Brands.  —  These  vary  according  to  the  source 
whence  they  are  derived;  the  various  lards  in  the 
American  market  are:  Neutral  Lard,  obtained  from 
the  "leaf"  by  rendering  at  a  low  temperature  (105° 
to  120°  F.),  used  in  making  butterine.  Only  a 
portion  of  the  fat  is  thus  extracted;  the  operation 
is  then  completed,  yielding  Leaf  Lard.  Choice  Lard 
is  obtained  from  some  parts  of  the  leaf  and  fat  from 


136  EXAMINATION  OF  CERTAIN  OILS. 

the  backs.  Prime  Steam  Lard  is  the  product  ob- 
tained from  the  trimmings,  head,  heart,  and  some 
intestinal  fat.  Gut  Grease  is  obtained  by  rendering 
all  the  other  parts  of  the  hog  except  the  heart, 
liver,  and  lungs.1 

Besides  these  products  obtained  from  the  live 
hog,  there  are  Butchers1  Lard  or  Crackling  Grease, 
obtained  from  scraps  and  trimmings,  and  White 
Grease  and  Brown  Grease,  which  are  obtained  from 
hogs  dying  in  transit,  being  prepared  from  the 
eviscerated  animal  and  its  viscera  respectively. 
Lastly,  there  is  Yellow  Grease,  a  product  of  the 
refuse  of  the  packing-houses. 

All  but  the  first  two  lards  are  pressed,  yielding 
an  oil  which  is  classed  according  to  its  color  as 
"Prime"  (very  light  straw)  to  "No.  2"  (brown). 

The  varieties  in  the  market  are  as  follows: 
"Prime"  Lard  oil,  prepared  from  Prime  Steam 
Lard;  "Pure"  Lard  oil,  from  No.  1  Lard  and 
White  Grease;  "Extra  No.  1,"  from  Light  Yellow 
Grease;  "No.  1,"  from  Yellow  Grease;  "No.  2," 
from  Brown  and  Gut  Grease;  and  "Crackling 
Oil,"  from  Crackling  Grease. 

Properties. — The  color  varies  from  very  light 
straw  to  brown,  and  the  odor  from  almost  none  to 
offensive  in  the  No.  2  lards. 

Composition. — Its  chemical  composition  is  largely 
olein,  with  admixture  of  stearin  and  palmitin. 


1  Condensed  from  "Lard  and  Lard  Adulterations,"  by  H.  W. 
Wiley,  U.  S.  Dep't  Agriculture,  Bull.  13,  1889,  p.  14. 


ANIMAL  OILS.  13? 

CONSTANTS. 

Sp  .Gr.  15°  C.        Maumene1.        Elaidin.  Iodine.        Saponification. 

.914-.916            39°  C.      Solid  cake.  60               195-6.1 

41°  72.5 2 

43°  75 3 

Various  parts  of  the  animal  give  oils  which  vary 
considerably;  the  iodine  values  of  oils  from  different 
sources  are  as  follows:4 

Leaf.         Intestine.         Back.         Foot.         Head. 
52.5-53        57.3  60.6        77.3          85 

Adulterants. — These  are  Cotton-seed,  Corn,  and 
Neutral  Petroleum  oils. 

Cotton-seed  oil  would  be  shown  by  the  Elaidin, 
Maumene,  and  Bechi  tests.  Corn  oil  would  be  in- 
dicated by  the  Maumene  test  (58)  and  Iodine  num- 
ber (115).  Petroleum  by  the  flash  test  and  lowering 
of  the  constants. 

Uses. — Lard  oil  is  used  as  a  burning  and  lubri- 
cating oil,  as  an  edible  oil,  and  for  oiling  textile 
material  preparatory  to  spinning. 

REFERENCE. 
WESSON,  Jour.  Am.  Chem.  Soc.,  17,  723-735  (1895). 

Tallow  Oil. — Preparation. — Tallow  oil  is  prepared 
by  pressing  tallow  after  the  manner  of  lard,  which  see. 

Properties. — It  is  a  light-yellow  bland  oil,  and  of 
an  odor  resembling  tallow. 

CONSTANTS. 

Sp.  Gr.  15°  C.        Maumene*.        Elaidin.         Iodine.        Saponification. 
.916  35         Solid  cake.      56  197 

1  No.  2  lard.    »  No.  1  lard.    '  Prime  lard.    4  Wiley,  toe.  cU. 


138  EXAMINATION  OF  CERTAIN  OILS. 

Uses. — It  is  used  to  mix  with  other  oils  and  as  a 
lubricant. 

Elain  or  Red  Oil.  —  Preparation. — Elain  oil,  or, 
as  it  is  sometimes  called,  " Saponified  Red  oil,"  is 
obtained  by  the  saponification  of  the  solid  fats  by 
the  lime,  sulphuric  acid,  or  water  methods.  The 
fatty  acids  thus  freed  from  their  combination  with 
glycerin  are  allowed  to  solidify  and  are  pressed. 
According  to  the  temperature,  more  or  less  stearic 
and  palmitic  acids  go  into  the  product;  these  can 
be  separated  by  distillation. 

It  is  oftentimes  semi-solid,  resembling  tallow;  the 
distilled  varieties  are  light  brown  to  deep  red. 

Composition. — Chemically  speaking,  it  is  nearly 
pure  oleic  acid. 

CONSTANTS.1 

Sp.  Gr.  15°  C.        Free  Fatty  Acids.         Iodine.        Saponification. 
.899-.908  80-97  90 2  200 

It  may  contain  some  unsaponifiable  matter,  con- 
sisting of  hydrocarbons  formed  in  the  process  of 
distillation;  these  may  vary  from  three  to  seven  per 
cent. 

Uses. — It  is  used  for  oiling  wool,  as  it  readily 
saponifies,  and  in  soap-making. 

1  Allen,  Lewkowitsch. 

*  Iodine  number  of  the  pure  acid. 


B.  WAXES. 


LIQUID  WAXES. 

Sperm  Oil — Preparation. — The  real  sperm  oil  is 
obtained  from  the  great  cavity  in  the  head  of  the 
sperm  whale;  it  is  often  mixed  with  the  oil  obtained 
from  the  body,  or  "  blubber  oil."  The  process  of 
manufacture  consists  in  chilling  the  crude  oil,  sepa- 
rating the  spermaceti  by  pressure,  and  bleaching  the 
expressed  oil  in  thin  layers  by  exposure  to  the  sun. 

Properties. — It  is  a  limpid,  pale-yellow  oil  of 
faint  odor  and  taste. 

Composition. — It  contains  no  glycerides  (Allen, 
Lewkowitsch),  but  is  a  mono-ester,  a  compound  of 
an  alcohol1  and  an  organic  acid.1  When  saponified 
these  alcohols  are  freed,  and  the  oil  yields  forty 
per  cent,  of  unsaponifiable  matter.  It  may  con- 
tain two  per  cent,  of  free  fatty  acids. 

CONSTANTS. 

Sp.  Gr.  15°  C.        Maumen<*.  Elaidin.  Iodine.     Saponification. 

.844-.S84        45°-47°C.        Solid  at  times.      81-90        123-147 
.880  (70) 

Adulterants. — Owing  to  its  high  cost  it  is  often 
adulterated,  Whale,  Mineral,  Rape,  Liver,  and 

1  Cetyl  alcohol,  Cie  HJJ  OH,  and  palmitic  acid  have  been  identified 
in  the  oil. 

139 


OF    THE 

UNIVERSITY 


140  EXAMINATION  OF  CERTAIN  OILS. 

Arctic  Sperm  (bottlenose  whale)  oil  being  used  for 
this  purpose. 

Whale  oil  would  be  shown  by  the  strong  fishy 
odor  and  " nutty"  taste,  also  by  the  raising  of  all 
the  constants.  Mineral  oils  would  be  indicated  by 
the  low  flash  point,  corresponding  to  a  gravity  of 
0.880,  and  by  the  lowering  of  the  constants.  Rape 
oil  by  the  high  Saponification  Value  (175)  and  the 
isolation  of  the  glycerin,  which  when  multiplied  by 
ten  gives  the  fatty  oils.  Liver  oils  would  be  revealed 
by  the  violet  coloration  with  sulphuric  acid  and 
rise  in  the  constants.  Arctic  Sperm  oil  might  be 
shown  by  the  taste. 

Uses. — It  is  employed  as  a  lubricant;  the  viscosity 
is  less  than  any  other  non-drying  fatty  oil,  and  also 
varies  less  than  any  other  oil  with  increase  of 
temperature. 

REFERENCES. 

STABBUCK,  "History  of  American  Whale  Fishery  from  Earliest 
Inception  to  1875." 

Report  of  U.  S.  Commissioner  of  Fisheries,  vol.  iv.,  1875. 
SCAMMON,  "Mammalia  of  North- Western  America." 


CHAPTER  VIII. 

RECOVERED  AND  WASTE  OILS  AND  FATS. 

THESE  have  assumed  more  importance  of  late 
in  this  country,  particularly  with  the  increasing 
requirements  of  boards  of  health  that  these  sub- 
stances be  kept  out  of  the  brooks  and  rivers.  Some 
of  them  are : 

Wool  Fat,  Fuller's  Grease, 

Distilled  Grease  Oleines,  Black  Oil, 

Sod  Oil,  Garbage  Grease. 
Cotton-seed  Foots, 

Wool  Fat — British,  German,  or  American  Degras; 
Suint;  Lanoline;  Wool,  Recovered,  or  Yorkshire 
Grease. 

Preparation. — As  the  names  denote,  this  is  the 
greasy  material  obtained  in  the  washing  of  wool:1 
wool  contains  from  30  to  80  per  cent,  of  impurities, 
made  up  of  (a)  wool  grease,  the  fatty  matter  secreted 
by  the  skin  of  the  sheep,  amounting  to  6  to  17  per 
cent,  of  the  wool;  (b)  suint,  also  a  skin  secretion 
but  soluble  in  water,  consisting  of  the  potassium 
salts  of  oleic,  valeric,  and  acetic  acids,  with  sul- 
phates, phosphates,  chlorides,  and  nitrogenous  com- 
pounds amounting  to  5  to  24  per  cent,  of  the  wool; 

1  For  a  detailed  description  of  wool- washing,  see  Thorp's  "Out- 
lines of  Industrial  Chemistry." 

141 


142  EXAMINATION  OF  CERTAIN  OILS. 

and  (c)  dirt,  earthy  matter,  and  manure.  These 
are  removed  in  two  ways,  by  scouring  with  soap 
and  alkali,  and  by  extraction  of  the  grease  with 
solvents,  usually  naphtha  or  carbon  tetrachloride, 
and  subsequent  washing.  These  foul  and  ill-smell- 
ing wash-waters  are  usually  run  into  the  streams 
and  form  one  of  the  most  troublesome  sources  of 
pollution.  Wool  grease  is  difficultly  saponifiable 
but  readily  emulsifiable  and  is  deposited  the  entire 
length  of  the  stream. 

To  recover  the  grease,  the  wash-waters  are  allowed 
to  stand,  to  settle  out  the  sand  and  dirt,  then 
"soured"  with  sulphuric  acid,  whereupon  part  of 
the  grease  floats  and  part  settles;  these  portions 
are  collected  and  pressed  hot  through  canvas. 
The  grease  thus  obtained  contains  besides  wool 
grease,  the  fatty  acids  of  the  soaps  used  and  also 
traces  of  sulphuric  acid.  Or  the  solvent  is  distilled 
off  from  the  solution  of  the  grease  and  the  latter 
strained  into  barrels.  The  product  thus  obtained 
is  of  lighter  color  and  better  quality  than  that  ob- 
tained in  the  acid  process,  is  free  from  sulphuric 
acid  and  practically  so  from  fatty  acids,  and  is  the 
only  one  to  which  the  term  wool  grease  is  properly 
applied. 

Properties. — It  is  a  light  or  dark  brown  substance 
of  peculiar,  unpleasant  odor  and  salvy  consistence; 
it  is  not  wholly  saponified  by  alcoholic  potash,  re- 
quiring sodium  alcoholate  to  complete  the  process. 
It  mixes  with  water  readily  and  forms  emulsions 
which  are  unusually  permanent,  particularly  if  any 


WASTE  FATS.  143 

alkali  be  present,  and  which  may  contain  as  much 
as  80  per  cent,  of  water.  It  is  not  readily  oxidized 
on  exposure  to  the  air. 

Composition. — It  is  a  complex  mixture  of  al- 
cohols and  esters,  a  collection  of  waxes  and  not  a 
fat:  the  esters  are  largely  those  of  cholesterol  and 
its  isomers.  Lanoceric,  lanopalmic,  myristic,  car- 
naubic,  and  other  oily  and  volatile  acids,  ceryl  and 
carnaubyl,  alcohol,  cholesterol,  and  isocholesterol 
are  some  of  the  compounds  which  have  been  found 

in  the  grease. 

CONSTANTS. 

From  what  has  been  said,  it  will  be  seen  that  it 
is  impossible  to  give  any  figures  to  which  the  name 
constant  can  properly  be  applied. 

Sp.  Gr.  Iodine.  Saponification. 

~^  0.9017  26  98-102 

lo.  o 

ANALYSIS  OF  WOOL  GREASE  IN  PER  CENT. 

Water.  Fatty  acids.  Neutral  oil.  Unsaponifiable. 

1  19-26  68-17  12-56 

Adulterants. — It  is  rarely  adulterated,  the  usual 
one  being  mineral  oil,  not  intentionally  added  but 
coming  from  the  wash-waters.  It  could  be  detected 
by  its  resistance  to  saponification  and  insolubility 
in  acetic  anhydride,  which  converts  the  cholesterol 
into  the  acetate.  Rosin  oil  might  also  be  used 
and  could  be  detected  by  partial  saponification 
with  potash,  the  object  being  to  saponify  the  rosin 
acids  in  the  oil  and  not  the  cholesterol  esters,  and 
the  liberation  of  the  rosin  acids,  which  are  submitted 
to  the  Liebermann-Storch  test. 


144  EXAMINATION  OF  CERTAIN  OILS. 

Uses. — Degras  is  used  to  mix  with  oils  for  curry- 
ing purposes,  with  lard  and  similar  oils  for  "wool 
oils,"  and  when  purified  forms  the  Lanoline  of  the 
Pharmacopoeia.  This,  from  the  ease  with  which 
it  is  absorbed  by  the  skin,  makes  an  admirable 
basis  for  salves  and  ointments.  There  are  two 
varieties,  one  anhydrous  (adeps  lanse),  and  one  with 
about  25  per  cent,  of  water  or  Lanoline  proper.  It 
is  used  to  replace  tallow  in  certain  cylinder  oils. 

Distilled  Grease. — Preparation. — This  is  prepared 
by  distilling  wool  grease  in  cast-iron  stills,  using 
superheated  steam  to  carry  forward  the  heavy 
vapors.  A  "stearine"  and  "oleine"  are  obtained 
by  cooling  and  pressing  the  distillate.  Wool  fat 
pitch  is  left  in  the  retort. 

Properties. — The  crude  stearines  are  brownish 
and,  like  all  these  products,  of  a  peculiar  penetrat- 
ing aldehydic  odor;  they  are  refined  and  are  then 
white  and  crystalline.  The  oleines  are  light  yellow 
to  dark  brown  and  have  a  greenish  fluorescence, 
which  must  not  be  mistaken  for  the  bluish  " bloom" 
of  the  mineral  oils  used  as  adulterants. 

Composition. — The  esters  originally  present  in  the 
wool  fat  are  broken  down  into  hydrocarbons  and 
fatty  acids  of  high  molecular  weight,  stearic,  pal- 
mitic, and  oleic,  which  in  turn  are  dissociated  into 
acids  of  lower  molecular  weight  and  other  hydro- 
carbons. The  following  equation,  cited  by  Smith,1 
gives  an  idea  of  what  may  have  taken  place: 

1  Ann.  China.  Phys.  (3),  6,  40. 


WASTE  FATS.  145 


l» 

Cetyl  palmitate  =  Palmitic  acid+Cetene 

The  nature  of  these  hydrocarbons  is  not  well 
understood;  it  is,  however,  probable  that  they  can 
be  distinguished  from  hydrocarbons  intentionally 
added  by  the  determination  of  the  bromine  addi- 
tion and  substitution  numbers,  the  optical  rotation, 
and  index  of  refraction.  These  constants,  obtained 
on  hydrocarbons  separated  from  some  distilled 
grease  oleines  by  Gill  and  Mason,1  are  shown  in  the 
table  below. 

Refractive 

Oleine.  Bromine.                    Optical           Index 

Sp.  Gr.  Addition.   Substitution.   Rotation,  at  20°  C. 

A 0.896  28.8            14.2         +17°  58'  1.4967 

BPure 0.902  25.1            14.8            17°36'  1.4991 

C 0.896  21.5            16.8            15°  13'  1.4948 

D  (doubtful  purity)  3.8              9.0              2°  56'  1.4921 

Mineral  oils  ..    . .  J°-848to       4'4to  5'6to  l°25'      L4662to 

10.863          5.9  8.4  1.4750 

The  extraction  of  the  unsaponifiable  matter  is 
carried  out  as  follows:  200  grams  of  the  oil  are 
saponified  by  boiling  on  a  water-bath  two  or  three 
hours  with  an  excess  of  alcoholic  potash  (120  grams 
to  the  liter)  in  a  750  cc.  flask,  provided  with  a  re- 
turn flow  condenser.  When  the  saponification  is 
complete  the  solution  is  transferred  to  a  liter  sep- 
aratory  funnel  and  shaken  several  times  with  300 
to  400  cc.  of  redistilled  gasolene  (86°  Be*).  The 
soap  solution  is  thrown  away.  The  gasolene  solu- 
tion is  concentrated  to  about  one-half  its  volume 


1 J.  Am.  Chem.  Soc.,  26,  665  (1904). 
10 


146  EXAMINATION  OF  CERTAIN  OILS. 

and  washed  with  warm  water  mixed  with  a  little 
alcohol  in  the  separatory  funnel  until  all  the  soap 
is  removed.  The  remainder  of  the  gasolene  is  dis- 
tilled off  in  the  water-bath,  and  the  residue  heated 
to  130°  C.  in  a  porcelain  dish  to  drive  off  the  water 
and  last  traces  of  gasolene. 

From  the  saponification  numbers  of  the  dif- 
ferent oils,  the  requisite  amount  of  alcoholic  pot- 
ash is  calculated,  and  100  per  cent,  excess  em- 
ployed. After  the  saponification,  when  gasolene 
was  first  added  and  the  mixture  thoroughly  shaken, 
no  separation  into  two  layers  occurred,  even  after 
several  hours'  standing.  Salt  was  added,  but  with- 
out effect.  Finally  water  was  added  in  small  quan- 
tities until  two  distinct  layers  formed.  In  washing 
the  gasolene  solution  water  alone  was  tried,  but 
did  not  appreciably  dissolve  the  soap.  When  warm 
water,  mixed  with  a  little  alcohol,  was  used  the 
soap  dissolved  readily.  In  heating  the  oil  to  130°  C. 
to  drive  off  water,  a  very  small  flame  or,  better,  an 
electric  stove  should  be  used,  and  the  oil  constantly 
stirred  to  prevent  bumping.  A  thermometer  serves 
well  as  a  stirring  rod. 

The  unsaponifiable  oil  is  freed  from  cholesterol 
and  other  higher  alcohols  by  boiling  for  an  hour 
with  100  cc.  of  acetic  anhydride  in  a  flask  provided 
with  a  return  flow  condenser,  and  heated  over  a 
sand-bath.  Water  is  added,  and  the  solution 
transferred  to  a  separatory  funnel,  where  it  is  washed 
with  water  and  alcohol  until  the  upper  layer  is  clear 
and  no  odor  of  acetic  acid  is  perceptible.  The  cho- 


WASTE  FATS.  147 

lesterol  and  higher  alcohols  are  dissolved  by  the 
acetic  anhydride,  leaving  the  hydrocarbons. 

After  submitting  the  oils  to  this  process,  a  deter- 
mination of  their  saponification  number  is  made, 
and  if  more  than  0.2  cc.  of  alcoholic  potash  is  used 
up,  the  treatment  with  alcoholic  potash  and  acetic 
anhydride  repeated. 

The  examination  of  distilled  wool  grease  is  con- 
ducted upon  the  same  general  lines  as  indicated  in 
the  case  of  wool  fat.  Lewkowitsch1  obtained  the 
following  results  : 

Free  fatty  acids 54.9  per  cent. 

Combined  fatty  acids,  glycerides 7.0    "      " 

Unsaponifiable  matter 38.8    "      " 

Some  distilled  grease  oleines  analyzed  by  the 
author  showed  the  following  composition: 

Free  fatty  acids  (oleic) 37%  47%       52%      37% 

Glycerides 33%  3%  18%       18% 

Unsaponifiable  matter 30%  51%  30%      45% 

Flash  point,  °F 364°  360°  370°  346° 

Adulterants. — The  only  adulterant  is  mineral 
oil,  the  detection  of  which  has  already  been  given. 

Uses. — Distilled  grease  stearine  is  used  in  soap 
and  candle  making;  the  oleine  is  used  as  a  "  wool  oil. " 

Sod  Oil,  Moellon,  French  Degras. — This  is  an  oil 
obtained  as  a  by-product  in  the  process  of  currying 
leather,  or  specially  prepared. 

Preparation. — The  skins  after  being  dehaired 
are  well  rubbed  with  fish  oil,  either  "cod,"  whale, 

1 J.  Soc.  Chem.  Ind.,  1 1,  141  (1892). 


148  EXAMINATION  OF  CERTAIN  OILS. 

or  menhaden,  and  thoroughly  stuffed  with  the  oil 
in  the  " stocks."  They  are  then  piled  in  heaps, 
whereby  a  kind  of  fermentation  or  "heating" 
ensues,  care  being  taken  that  the  temperature  does 
not  rise  too  high,  the  process  being  complete  when 
the  leather  assumes  the  well-known  yellow  color 
of  chamois  leather.  It  is  well  scraped  with  a 
blunt  knife,  washed  with  soda  or  potash,  the  emul- 
sion treated  with  acid,  and  the  oil  which  rises 
to  the  surface  is  added  to  that  obtained  by 
scraping. 

Properties. — It  is  a  light  or  dark  brown  oil  of 
peculiar  odor,  betraying  its  origin. 

Composition. — Prepared  in  the  way  indicated, 
its  composition  must  naturally  be  very  varied; 
besides  unchanged  oil  and  free  fatty  acids,  it  con- 
tains a  resinous  substance  or  "degras-former,"  prob- 
ably a  mixture  of  oxidized  oils  and  their  anhydrides. 
Jean1  states  that  this  is  soluble  in  alcohol  and  ether, 
insoluble  in  petroleum  spirit,  and  is  saponifiable, 
but  the  soap  is  not  precipitable  by  salt.  Moellon 
also  contains  unsaponifiable  matter  coming  from 
the  oils  used  in  its  preparation. 

The  following  shows  the  results  of  the  examina- 
tion of  12  sod  oils  found  on  the  American  market 
by  Hopkins,  Coburn,  and  Spiller.2  The  results  are 
calculated  in  per  cent,  on  the  water-free  oil  and 
the  acids  in  milligrams  of  KOH  per  gram  of  oil. 


1Mon.  sci.,  15  (1889). 

2  J.  Am.  Chem.  Soc.,  21,  291  (1899). 


WASTE  FATS. 

149 

ij 

i 

« 

k 

i 

ll 

o.S 

Hide 
Fragmenl 

IJ 

Oxidized 
Acids. 

Free  Fati 
Acids. 

0.05 

1.1 

56.6 

0.7 

0.15 

0.4 

1.1 

32.6 

1.0 

91.5 

96.6 

8.8 

3.0 

42.6 

26.4 

34.3 

I 

Minimum.          1.0 
Maximum.       40.6 

Examination  and  Adulterants. — The  determina- 
tions to  be  made  upon  sod  oil  are  indicated  above; 
that  of  water  is  effected  by  mixing  five  grams 
of  the  sample  with  sand  until  a  solid  mass  is 
obtained  and  drying  at  110°  C.  It  usually  con- 
tains unchanged  oil  which  is  added  to  it  after  its 
formation,  this  cannot  properly  be  regarded  as  an 
adulteration.  Mineral  and  rosin  oils  may  sometimes 
be  found  in  it,  obviously  added  with  fraudulent 
intent.  The  specific  gravity  of  the  water-free  degras 
is  higher  than  that  of  the  oils  from  which  it  is  made; 
it  varies  from  0.945  to  0.955,  and  if  it  be  as  low  as 
0.920  an  admixture  with  mineral  oil  is  indicated. 

Uses. — It  is  used  for  currying  leather. 

Oil  Foots. — Preparation. — The  term  " foots"  is  ap- 
plied by  the  oil  and  paint  trade  to  any  sediment 
obtained  in  the  manufacturing  or  storing  process.  It 
is  a  mixture  of  oil,  the  impurities  contained  in  the  oil 
coming  from  the  seed,  or  "  mucilage/'  as  it  is  called, 
coloring  matter,  water,  dirt,  and  where  alkali  has 
been  used  in  the  refining  process,  of  the  saponified 
oil  or  soap. 

Properties. — Cotton-seed  oil  foots1  or  soap-stock 
varies  in  color  from  light,  dirty  yellow,  through 

1  Wesson,  J.  Soc.  Chem.  Ind.,  26,  595  (1907). 


150  EXAMINATION  OF  CERTAIN  OILS. 

dark  green  to  deep  red,  changing  to  black  on  ex- 
posure to  the  air.  The  odor  is  that  of  decomposed 
fish,  due  probably  to  methyl  amine.  If  it  contains 
more  than  40  per  cent,  of  water  it  ferments  easily 
in  hot  weather  and  the  soap  made  therefrom  is 
poorer  in  color  than  that  made  from  the  fresh  stock. 

Composition  and  Analysis. — This  has  been  given 
under  preparation;  it  varies  with  the  amount  and 
strength  of  the  alkalies  used:  the  total  fatty  acids 
vary  from  35  to  65  per  cent.,  45  being  a  fair  average; 
less  than  40  per  cent,  cannot  be  delivered  on  con- 
tracts. The  specific  gravity  is  from  0.97  to  1.04, 
1.00  being  the  average. 

A  typical  analysis  is  as  follows: 

Water 36.0 

Fatty  anhydrides 48.5 

Glycerine 4.0 

Caustic  soda,  Na20 3.2 

Color 2.4 

Organic  matter 5.8 

Uses. — It  is  used  for  the  manufacture  of  soap, 
textile  or  mill  soaps  particularly,  and  is  by  far  the 
cheapest  soap-making  material  on  the  market. 
Many  of  the  "washing  powders "  are  composed  of 
settled  foots  soap  and  soda  ash.  In  England  the 
foots  are  distilled  with  superheated  steam  after  the 
manner  of  wool  grease,  which  has  already  been  de- 
scribed: an  oleine,  stearine,  and  cotton-seed  stearine 
pitch  are  the  products.  Other  foots  beside  cotton- 
seed are  linseed,  whale,  sperm,  and  olive  oil. 

Fuller's  Grease.— " Seek  oil"  (England),  Recov- 
ered Oil. 


WASTE  FATS.  151 

Preparation. — This  is  obtained  from  the  water 
in  which  woolen  cloth  has  been  washed,  by  a  pro- 
cess exactly  similar  to  that  by  which  wool  fat  is 
produced.  It  consists,  therefore,  of  the  oil  which 
has  been  used  in  carding  and  spinning  the  wool, 
together  with  the  fatty  acids  obtained  from  the 
scouring  soap  used,  and  those  which  existed  in  the 
oils  as  such.  Olive,  lard,  neat's-foot,  saponified, 
and  distilled  red,  or  "elaine  oils/'  "  distilled  grease," 
oleines  and  mineral  oils,  sometimes  mixed  with  wool 
fat  or  degras,  are  some  of  the  oils  used  for  this  pur- 
pose, or  "wool  oils." 

Composition. — This  will  vary  according  to  the 
oils  and  soaps  used,  and  the  results  obtained  should 
be  compared  with  the  constants  of  the  oils  origi- 
nally employed.  If  the  oil  is  to  be  used  again  as  a 
wool  oil  the  spontaneous  combustion  and  saponi- 
fication  tests  should  be  applied. 

Black  Oil. — This  is  the  term  applied  to  oil  ex- 
tracted from  the  greasy  waste  of  woolen  mills  and 
is,  except  for  mineral  oil  coming  from  the  machinery, 
the  same  as  that  upon  the  wool  itself.  It  should 
not  be  confounded  with  a  petroleum  product,  black 
oil,  a  crude  petroleum  from  which  naphtha  and  burn- 
ing oil  have  been  distilled  and  used  for  freight-car 
lubrication. 

Garbage  Grease. — This  is  a  grease  obtained  by 
the  extraction  of  garbage  with  naphtha  or  carbon 
tetrachloride.  It  is  used  for  the  manufacture  of 
cheap  toilet  soaps,  or  distilled  as  is  wool  fat. 


APPENDIX. 

TABLES,  REAGENTS,  AND  RAILROAD  SPECIFICATIONS. 


TABLE  I. 

Requirement  of  Various  States  and  Cities  regarding  Flash  and  Fire 
Test  of  Illuminating  Oils. 

Name.                                    Flash,  °F.     Fire,  °F.  Instrument. 

Arkansas 130  Tagliabue. 

Columbia,  District  of 120 

Connecticut 110 

Florida 130  Tagliabue. 

Georgia 120 

Illinois 150  Tagliabue. 

Indiana 120  . . .  Indiana. 

Iowa 105  ...  Elliott. 

Kansas 110  Tagliabue. 

Kentucky 130 

Louisiana 125  . . .  Tagliabue. 

Maine 120  . . .  Tagliabue  open. 

Massachusetts 100  ...  Tagliabue  open. 

Michigan 120  148  Foster. 

Minnesota 110  . . .  Minnesota. 

Missouri 150  Tagliabue. 

Montana 110 

Nebraska 100  ...  Foster. 

New  Hampshire 100  120  Tagliabue. 

New  Jersey 100  115 

New  Mexico 150 

New  York 110  Tagliabue. 

North  Carolina 100  ...  Foster. 

North  Dakota 100 

Ohio 120  ...  Foster. 

153 


154 


APPENDIX. 


Name.                                  Flash,  °F.  Fire,  °F.  Instrument. 

Pennsylvania 110  Tagliabue. 

Rhode  Island 110 

South  Dakota 110  ...  Foster. 

Tennessee 120  ...  Open  cup. 

Vermont 110  Tagliabue. 

Wisconsin 120  . . .  Wisconsin. 

Requirements  of  Cities  where  Different  from  State  Law. 

Name.                                    Flash,  °F.  Fire,  °F.  Instrument. 

Baltimore,  Md 120 

Denver,  Col 110  ...  Tagliabue  open. 

Los  Angeles,  Cal 110  ...  Tagliabue  open. 

Meriden,  Conn 125 

Milwaukee,  Wis 110 

Newark,  N.  J 110 

New  Haven,  Conn 110  Tagliabue  open. 

New  Orleans,  La 110  Tagliabue  open. 

New  York,  N.  Y 100  ...  Elliott. 

Richmond,  Va 110  Tagliabue. 

Sacramento,  Cal 110  ...  Tagliabue  open. 

San  Francisco,  Cal 100  . . .  Tagliabue  open. 

Wilmington,  Del 110 


TABLE  II. 

Showing  the  Flash  and  Fire  Test  of  Various  Oils.1 


Flash,      Flash,        Fire,        Fire, 


Name.  °  C. 

Corn 249 

Cotton-seed 305 

Prime  Lard 264 

No.  2  Lard 215 

Boiled  Linseed 192 

Raw  Linseed 274 

Menhaden 

Neat's-foot..  .  226 


480 

582 

T530 

1600 

419 

378 

525 

405 

439 


335 
340 

340 

242 
300 
340 

273 


635 
644 

644 

468 
572 
644 
484 
523 


1  Done  with  the  apparatus  described  upon  page  40. 


APPENDIX  155 

Flash,  Flash,  Flash,  Fire, 

Name.                                                 °C.  °F.  °F.  °F. 

Olive 233  451  283  541 

25°  Paraffine 210  410  246  475 

75%  25°  Paraffine,  25%  Neat 's-foot. . .  210  410  244  471 

75%  25°  Paraffine,  25%  Lard 210  410  254  489 

50%  25°  Paraffine,  50%  Lard 218  423  267  513 

25%  25°  Paraffine,  75%  Lard 227  441  284  543 

Distilled  Red 184  364  213  415 

Sperm  No.  1 220  428  270  518 

Sperm  No.  2 252  486  301  574 


Flash  Point  of  Certain  Organic  Compounds. 

Flash,  Fire, 


Name.  °C.*  "F.1          °F.4       °F.'       *F.8 

81  53    54  62 


Alcohol,  +  0.5%  ether  

...       9 

75 

.. 



Alcohol,  4%  by  vol  

...     68 

181 



Benzene,  CeH6  

...     -8 

45 



Turpentine  

.  .  .     92-98 

119-125 

90 

95 

100 

83-89  s 

Methyl  Alcohol  

45 

52 

56 

Denatured  Alcohol  

55 

50 

58 

Arptonfi 

34 

iRaikow  Chem.  Ztg.  (1899),  145:  Holde  and  Pelgry,  Chem.  Centralb.  (1899) 
2,  546.  Done  with  Abel's  tester  and  calculated  to  Massachusetts  tester  by 
adding  27°  F. 

*  Abel  tester. 

»  Done  in  author's  laboratory  with  N.  Y.  tester. 

'Schieffelin,  J.  Soc.  Chem.  Ind.,  27,  922  (1908),  with  Mass,  open  tester. 

» McCandless,  J.  Am.  Chem.  Soc.,  26,  982  (1904). 


156 


APPENDIX. 


TABLE  III. 

Relation  of  Baume  Degrees  to  Specific  Gravity  and  the  Weight  of  One 
United  States  Gallon  at  60°  F. 


1 

£ 

P 

Pounds  in 
Gallon. 

Baume*. 

Specific 
Gravity. 

Pounds  in 
Gallon. 

Baume. 

>> 

ll 

8P 

OQ 

Pounds  in 
Gallon. 

Baumd. 

Specific 
Gravity. 

Pounds  in 
Gallon. 

10 

1.0000 

8.33 

31 

0.8695 

7.24 

52 

0.7692 

6.41 

73 

0.6896 

5.75 

11 

0.9929 

8.27 

32 

0.8641 

7.20 

53 

0.7650 

6.37 

74 

0.6863 

5.72 

12 

0.9859 

8.21 

33 

0.8588 

7.15 

54 

0.7608 

6.34 

75 

0.6829 

5.69 

13 

0.9790 

8.16 

34 

0.8536 

7.11 

55 

0.7567 

6.30 

76 

0.6796 

5.66 

14 

0.9722 

8.10 

35 

0.8484 

7.07 

56 

0.7526 

6.27 

77 

0.6763 

5.63 

15 

0.9655 

8.04 

36 

0.8433 

7.03 

57 

0.7486 

6.24 

78 

0.6730 

5.60 

16 

0.9589 

7.99 

37 

0.8383 

6.98 

58 

0.7446 

6.20 

79 

0.6698 

5.58 

17 

0.9523 

7.93 

38 

0.8333 

6.94 

59 

0.7407 

6.17 

80 

0.6666 

5.55 

18 

0.9459 

7.88 

39 

0.8284 

6.90 

60 

0.7368 

6.14 

81 

0.6635 

5.52 

19 

0.9395 

7.83 

40 

0.8235 

6.86 

61 

0.7329 

6.11 

82 

0.6604 

5.50 

20 

0.9333 

7.78 

41 

0.8187 

6.82 

62 

0.7290 

6.07 

83 

0.6573 

5.48 

21 

0.9271 

7.72 

42 

0.8139 

6.78 

63 

0.7253 

6.04 

84 

0.6542 

5.45 

22 

0.9210 

7.67 

43 

0.8092 

6.74 

64 

0.7216 

6.01 

85 

0.6511 

5.42 

23 

0.9150 

7.62 

44 

0.8045 

6.70 

65 

0.7179 

5.98 

86 

0.6481 

5.40 

24 

0.9090 

7.57 

45 

0.8000 

6.66 

66 

0.7142 

5.95 

87 

0.6451 

5.38 

25 

0.9032 

7.53 

46 

0.7954 

6.63 

67 

0.7106 

5.92 

88 

0.6422 

5.36 

26 

0.8974 

7.48 

47 

0.7909 

6.59 

68 

0.7070 

5.89 

89 

0.6392 

5.33 

27 

0.8917 

7.43 

48 

0.7865 

6.55 

69 

0.7035 

5.86 

90 

0.6363 

5.30 

28 

0.8860 

7.38 

49 

0.7821 

6.52 

70 

0.7000 

5.83 

95 

0.6222 

5.18 

29 

0.8805 

7.34 

50 

0.7777 

6.48 

71 

0.6965 

5.80 

30 

0.8750 

7.29 

51 

0.7734 

6.44 

72 

0.6930 

5.78 

APPENDIX. 


157 


TABLE  IV. 

Showing  the  Specific  Gravity,  Degrees  Baume,  and  Weight  per  Gallon 
and  per  Cubic  Foot  of  Certain  Oils. 


Specific 
Gravity. 

Degrees 
Baume*. 

Pounds  in 
One 
Gallon. 

Pounds 
in  One 
Cubic 
Foot. 

Water 

1  0000 

10 

8.33 

62.50 

Castor  Oil 

.9639 

15 

803 

60.24 

Linseed  Oil  boiled 

.9411 

19 

784 

58.81 

Linseed  Oil  raw 

.9299 

21 

7.75 

58.12 

Menhaden,  light                     .... 

.9325 

20 

7.77 

58.28 

Menhaden,  dark        

.9292 

21 

7.74 

58.08 

Hemp-seed           

.9307 

20 

7.75 

58.17 

Cod  Liver                

.9270 

21 

7.72 

57.94 

Whale             

.9254 

21 

7.71 

57.84 

PoDDv-seed 

.9243 

21 

7.70 

57.77 

Cotton-seed  

.9220 

22 

7.67 

57.53 

Fish  

.9205 

22 

7.67 

57.53 

Olive  

.9192 

22 

7.65 

57.45 

Almond  

.9180 

23 

7.65 

57.38 

Lard 

9175 

23 

7  64 

5734 

Rape-seed  

.9155 

23 

7.63 

57.22 

Neat's-foot  

.9142 

23 

7.62 

57.14 

Colza  

.9136 

23 

7.61 

57.10 

Palm  

.9046 

25 

7.54 

56.54 

Sperm  natural 

8815 

29 

7.34 

55.09 

Sperm  bleached 

.8813 

29 

7.34 

55.08 

Spirits  of  Turpentine 

.8600 

33 

7.16 

53.75 

Alcohol  90  per  cent 

.8228 

40 

6.85 

51.43 

Alcohol  95  per  cent 

.8089 

43 

6.74 

50.56 

Alcohol  absolute                .    ... 

.7938 

46 

6.61 

49.61 

NOTE. — In  the  columu  marked  Baume",  the  nearest  whole  number  is  given, 
omitting  fractions. 


158 


APPENDIX. 


TABLE  V. 
Comparison  of  SayboU's  A  Viscosimeter  and  Doolittle's  Viscosimeter. 

Saybolt.  Doolittle. 
Grams  of 

Oil.                                            Specific  Gravity.  Seconds.  Sugar. 

StoveGasolene 680             23  0.0 

Water 1.000              25  0.0 

Kerosene,  150°  Fire  Test 783              26.8  3.3 

Lantern,  300°  Fire  Test 827              36.4  49.8 

Spindle 849              57.9  62.8 

Spindle 851              60  65.5 

Sperm 880  102  73.5 

Spindle 863  115  74.3 

Spindle 879  138  77.0 

Spindle 868  156  78.4 

Loom 888  203  80.6 

Lard 916  215  82.8 

Mineral 907  224  83.5 

Neat's-foot 916  250  83.7 

25°Paraffine 900  272  84.2 

Mineral..                            903  339  86.0 


NOTE. — Table  V.  was  made  from  data  obtained  in  the  author's  laboratory; 
Tables  VI.  and  VII.  are  from  those  issued  by  George  D.  Feidt  &  Co.,  Philadel- 
phia, former  makers  of  the  torsion  instrument. 

The  results  of  Tagliabue's  instrument  should  agree  very  closely  with  those 
obtained  by  the  use  of  Sayboit's. 


APPENDIX 


159 


TABLE  VI. 
A  Comparison  of  Saybolt  B  and  Torsion  Viscosimeters,  at  70°  F. 


Saybolt  B. 
Seconds. 

Torsion 
Grams  Sugar 
per  100  cc. 
Solution. 

(Differ- 
ence) 
Grams 
Sugar. 

Saybolt  B. 
Seconds. 

Torsion 
Grams  Sugar 
per  100  cc. 
Solution. 

(Differ- 
ence) 
Grams 
Sugar. 

Uf 

0.0 

56 

83.2 

.2 

15 

9.2 

9.2 

57 

83.4 

.2 

16 

22.5 

14.3 

58 

83.6 

.2 

17 

36.5 

14.0 

59 

83.8 

.2 

18 

47.7 

11.2 

60 

84.0 

.2 

19 

53.5 

6.8 

61 

84.2 

.2 

20 

57.7 

4.2 

62 

84.35 

.15 

21 

60.6 

2.9 

63 

84.5 

.15 

22 

63.2 

2.6 

64 

84.65 

.15 

23 

65.6 

2.4 

65 

84.8 

.15 

24 

67.5 

1.9 

66 

85.0 

.2 

25 

69.2 

1.7 

67 

85.15 

.15 

26 

70.6 

1.4 

68 

85.3 

.15 

27 

71.6 

1.0 

69 

85.45 

.15 

28 

72.6 

1.0 

70 

85.6 

.15 

29 

73.4 

.8 

71 

85.75 

.15 

30 

74.0 

.6 

72 

85.9 

.15 

31 

74.6 

.6 

73 

86.0 

.1 

32 

75.2 

.6 

74 

86.15 

.15 

33 

75.6 

.4 

75 

86.25 

.1 

34 

76.0 

.4 

76 

86.35 

.1 

35 

76.5 

.5 

77 

86.45 

.1 

36 

76.9 

.4 

78 

86.55 

.1 

37 

77.4 

.5 

79 

86.65 

.1 

38 

77.8 

.4 

80 

86.75 

.1 

39 

78.2 

.4 

85 

87.25 

.50 

40 

78.6 

.4 

90 

87.60 

.35 

41 

79.0 

.4 

95 

87.8 

.20 

42 

79.3 

.3 

100 

88.0 

.2 

43 

79.7 

.4 

105 

88.1 

.1 

44 

80.1 

.4 

110 

88.2 

.1 

45 

80.4 

.3 

115 

88.3 

.1 

46 

80.75 

.35 

120 

88.4 

.1 

47 

81.0 

.25 

125 

88.5 

.1 

48 

81.3 

.3 

130 

88.6 

.1 

49 

81.6 

.3 

135 

88.7 

.1 

50 

81.85 

.25 

140 

88.8 

.1 

51 

82.2 

.35 

145 

88.9 

.1 

52 

82.4 

.2 

150 

89.0 

.1 

53 

82.6 

.2 

155 

89.05 

.05 

54 

82.8 

.2 

160 

89.10 

.05 

55 

83.0 

.2 

NOTE.— Saybolt  viscosimeter  used  gave  a  viscosity  at  70°  F.  of  371  seconds 
for  pure  sperm  oil  of  .886  specific  gravity. 


160 


APPENDIX. 


TABLE  VII. 

A  Comparison  of  Saybolt  C  and  Torsion  Viscosimeters,  at  212°  F. 


Saybolt'C. 
Seconds. 

Torsion 
Grams  Sugar 
per  100  cc. 
Solution. 

(Differ- 
ence) 
Grams 
Sugar. 

Saybolt  a 
Seconds. 

Torsion 
Grams  Sugar 
per  100  cc. 
Solution. 

(Differ- 
ence) 
Grams 
Sugar. 

23 

48.1 

60 

65.75 

.2 

24 

49.2 

1.1 

61 

65.95 

.2 

25 

50.25 

1.05 

62 

66.1 

.15 

26 

51.3 

1.05 

63 

66.25 

.15 

27 

52.3 

1.0 

64 

66.40 

.15 

28 

53.2 

.9 

65 

66.6 

.20 

29 

54.0 

.8 

66 

66.8 

.2 

30 

54.75 

.75 

67 

67.0 

.2 

31 

55.5 

.75 

68 

67.2 

.2 

32 

56.2 

.7 

69 

67.3 

.1 

33 

56.85 

.65 

70 

67.5 

.2 

34 

57.5 

.65 

71 

67.7 

.2 

35 

58.0 

.5 

72 

67.8 

.1 

36 

58.5 

.5 

73 

68.0 

.2 

37 

59.0 

.5 

74 

68.2 

.2 

38 

59.45 

.45 

75 

68.3 

.1 

39 

59.85 

.40 

76 

68.45 

.15 

40 

60.25 

.40 

77 

68.60 

.15 

41 

60.6 

.35 

78 

68.75 

.15 

42 

60.9 

.3 

79 

68.95 

.2 

43 

61.25 

.35 

80 

69.1 

.15 

44 

61.6 

.35 

85 

69.9 

.8 

45 

61.95 

.35 

90 

70.6 

.7 

46 

62.3 

.35 

95 

71.3 

.7 

47 

62.6 

.3 

100 

71.9 

.6 

48 

62.9 

.3 

105 

72.4 

.5 

49 

63.2 

.3 

110 

72.9 

.5 

50 

63.45 

.25 

115 

73.3 

.4 

51 

63.7 

.25 

120 

73.7 

.4 

52 

64.0 

.3 

125 

74.0 

.3 

53 

64.3 

.3 

130 

74.2 

.2 

54 

64.5 

.2 

135 

74.4 

.2 

55 

64.7 

.2 

140 

74.6 

.2 

56 

64.9 

.2 

145 

74.8 

.2 

57 

65.15 

.25 

150 

74.9 

.1 

58 

65.35 

.20 

155 

74.95 

.05 

59 

65.55 

.2 

160 

75.0 

.05 

NOTE. — Saybolt  viscosimeter  used  gave  a  viscosity  at  212°  F  of  36$  seconds 
for  pure  sperm  oil  of  .884  specific  gravity. 


APPENDIX. 


161 


TABLE  VIII. 

Comparison  of  Sayboli's  A  and  the  Engler  Viscosimeter. 

Seconds. 

Saybolt  A.  Engler. 

Water 22.9  52.0 

Neutral 46.1  119. 

XX  Wool 105.2  320.5 

Paraffine 127.2  379. 

Spindle 147.0  437.0 

Lard..  .  216.7  686.0 


TABLE  IX. 

Showing  the  Principal  Constants  of  Various  Oils. 


od 

-8 

g-g 

NAME. 

E 

O 

Vajenta, 

Elaidin. 

I 
t 

|| 

Refraction 
Index, 
15°-15.5°  C. 

|S 

03 

5 

eg 

Almond  

.918 

110 

53 

Solid. 

97 

190 

1.4728 

Castor 

963 

Soluble  * 

47 

84 

181 

1  4795-4803 

Chinese  Wood.  .  .  . 

.940 

40-47 

163 

193 

1.503s 

8741 

9 

260 

1  4573 

Colza.  (See  Rape) 

Corn 

922 

80 

85 

Pasty 

115 

191 

1  4768 

Cotton-seed  

.922 

902-110 

76 

Pasty. 

108 

193 

1.4737-4757 

Elain 

904 

903 

200 

1  4631  T 

Horse... 

.919 

54  68  80 

5? 

80 

197 

1.  4652-1  .47047 

Lard 

917 

54  66  98 

41 

Very  solid. 

65 

195 

1  4694 

Linseed  

.934 

572-74  70-79 

111 

176 

191 

1.4835 

Maize.  (See  Corn) 

Menhaden  

.930 

642 

1  2fi 

154 

190 

1  .4783  7 

Neat's-foot  

.915 

62  72-75 

46 

Solid.s 

71 

194 

1.4695-4705 

Olive  

.916 

85-111 

35 

Very  solid. 

8? 

194 

1.4703-4713 

Palm 

859 

52 

199 

1  410  at  60°F 

Peanut  

.917 

872-112 

51 

Solid. 

P8 

194 

1.4731 

Poppy-seed  

.925 

87 

138 

193 

1.4773 

Rape  

.916 

Insoluble. 

55 

Pasty. 

101 

174 

1.4720-4757 

Sesame1  

.923 

872-107 

65 

Pasty. 

107 

190 

1.4748-4762 

Sperm  

.880 

Insoluble. 

46 

Solid. 

85 

135 

1.4664-4673 

Sunflower  

.925 

71 

125 

192 

1.4762 

TaUow 

916 

71-75 

Solid. 

56 

197 

1  4660  7 

Whale  

.927 

88 

190 

1  4691  7 

iAt99°C. 
<Cold. 
7  At  25°  C. 


'Allen. 
6  At  times. 


3  Pure  oleic  acid. 
•At  19°. 


11 


162 


APPENDIX. 


TABLE  X. 

Volumetric  Factors. 
1  Cc.  5  HC1=. 018185  Gm.  HC1. 
1  Cc.  A  HC1  =  . 003637  Gm.  HC1. 
1  Cc.  |  KOH  =  .028  Gm.  KOH. 

1  Cc.  {?  KOH  =  .047  Gm.  oleic  acid  =  .008133  Gm.  H2SO4. 
1  Cc.  -nr  KOH  =  .0056  Gm.  KOH. 
ICc.  K2Cr2O7  3.8747  Gm.  per  liter  =  .0038747  Gm.  K2Cr2O7  =  .010 

Gm.  I. 
1  Cc.  -nr  NaaS  A  +  5HSO  =  .0248  Gm.  Na^A  +  5H2O  =  .01265  Gm.  I. 


TABLE  XI. 

The  Action  of  Oils  upon  Metals.1 
A.  OILS. 

Least  Most 

Name.                           No  Action  on                Action  on  Action  on 

Cotton-seed  ...................             Lead.  Tin. 

Lard  .........................            Zinc.  Copper. 

Mineral  ............     Zinc.                        Brass.  Lead. 

Olive  .........................            Tin.  Copper. 

Rape  ..............     Brass  and  Tin.        Iron.  Copper. 

Seal  ..........................             Brass.  Copper. 

Sperm  ........................             Brass.  Zinc. 

Tallow  .......................             Tin.  Copper. 

Whale  .............     Tin.                         Brass.  Lead. 


B.  METALS. 


Name.  No  Action  on 

Brass  .............  Rape. 

Copper  ............  Mineral. 

Iron 
Lead 

Tin  ...............  Rape. 

Zinc  ..............  Mineral. 


Least 
Action  on 
Seal. 
Sperm. 
Seal. 
Olive. 
Olive. 
Lard. 


Most 

Action  on 
Olive. 
Tallow. 
Tallow. 
Whale. 
Cotton-seed. 
Sperm. 


il.  J.  Redwood,  J.  Soc.  Chem.  Ind.,  5,  362  (1886). 

For  the  action  of  oil  upon  cement,  see  id.,  42,  970  (1905). 


APPENDIX. 


163 


TABLE  XII. 

Showing  the  Principal  Constants  of  Fatty  Acids  derived  from  Various 

Oils. 

Melting 

Name.  Point. 

Almond 14°  C. 

Castor 13 

Cocoanut 25-27 

Corn 18-21 

Cotton-seed 35-43 

Horse 25-39 

Lard 35 

Linseed 17-24 

Neat's-foot 17-26 

Olive 19-28.5 

Palm 47-50 

Peanut 28-33 

Poppy-seed 20 

Rape 16-22 

Sesame* 21-32 

Sperm 13-21 

Sunflower 17-24 

Tallow 34-37 

Whale...  .  16 


Sap.  Value. 
204 

Molee. 
Weight. 

Iodine 
Value. 
95 

290-295 

87-88 

258 
1984 

200 

8-9 
113-125 

202-208 
203 

275-289 

110-116 

72-87 

197 
200-206 

283-307 

179-209 
60-77 

193 
206 
202 
199 

280-286 
270 

282 

86-104 
53 
97 
116-139 

185 
200 

314 
286 
281-305 

96-106 
109-112 
83-88 

201 

124-134 

56 

131 

TABLE  XIII. 

Showing  the  Bromine  Addition  and  Substitution  Figures. 
Mcllhiney's  Method  (page  63). 

Total.  Addition.  Substitution.    Iodine. 

Benzine1 51.5  15.5  18.0          

Benzine1 6.3  2.7  1.8          

Cocoanut  Oil 5.4  4.7  0.3          

Cotton-seed 65.8  62.2  1.8  ..... 

Corn.    ( See  Maize.) 

Linseed,  average 112.0  106.6  2.7  183.8 


1  Substitutes  for  turpentine. 


164 


APPENDIX. 


Total.  Addition.  Substitution.   Iodine* 

Linseed,  boiled,  average 109.5  103.0  3.2          

Maize,  average 75.8  72.9  1.5          

Menhaden,  average 110.6  95.6  7.5  174.9 

Paraffine,  hard 3.5  1.4  1.1          

Petroleum,  neutral 14.4  6.4  4.0          

Rosin,  w.  g 161.4  8.0  76.7          

Rosin,  black 135.4  5.4  65.0          

Rosin  Oil 92.3  7.7  42.3  63.9 

Rosin  Oil,  third  run 197.6  16.4  90.6           

Tallow 24.0  21.5  1.3          

Turpentine 266.1  166.1  50.0          


TABLE  XIV. 

Showing  a  Comparison  of  the  Iodine  Numbers  obtained  by  Various 

Methods. 


Oil. 

Hiibl. 

Hanus. 

Wijs. 

Butter  

35.3 

35.3 

36.22 

Castor  

82.6 

84.4 

85.61 

Cod  

148.5 

147.5 

154.61 

Cotton-seed  

108.5 

107.0 

110.01 

Cocoanut  

8.9 

8.6 

9.02 

Corn  

119.0 

120.2 

123.22 

Lard  

70.0 

69.7 

2 

Linseed  

179.5 

183.7 

188.72 

Oleomargarine  

66.3 

64.8 

66.02 

Oleomargarine  

52.5 

52.0 

52.92 

Oleomargarine  

89.8 

90.0 

91.41 

Olive  

79.2 

80.6 

79.92 

Peanut  

96.3 

97.4 

99.02 

Poppy-seed  

133.4 

132.9 

135.22 

Rape  

100.2 

102.8 

104.12 

Sesame"  

106.4 

106.5 

107.02 

Sunflower  

106.4 

107.2 

109.22 

Whale  

120.2 

120.7 

124.81 

iHunt,  J.  Soc.  Chem.  Ind.,  21,  454  (1902). 

>Tolman  and  Munson,  J.  Am.  Chem.  Soc.,  25,  244  (1903). 


APPENDIX.  165 

REAGENTS. 

The  reagents  used  in  oil  analysis  are  few  and 
easily  obtained.  A  list  and  their  method  of  prepa- 
ration is  here  given. 

Acetic  Acid,  Glacial. — Baker  and  Adamson's  C.  P.  or  Kahl- 
baum's  "Eisessig,"  ninety-nine  and  five-tenths  per  cent.  pure. 
The  determination  of  its  strength  should  be  made  by  titration 
and  not  by  specific  gravity,  as  the  ninety-eight  per  cent,  and  eighty 
per  cent,  acid  have  the  same  specific  gravity,  1.067.  The  deter- 
mination of  the  melting  point  gives  results  equally  good  with 
those  obtained  by  titration  and  requires  less  time.1  It  is  made  after 
the  manner  of  the  "titer  test"  (p.  82),  the  tube  being  half  filled, 
chilled  to  10°  or  11°  C.,  and  further  chilled  by  placing  the  outside 
bottle  in  ice-water;  the  temperature  of  the  super-cooled  acid  rises 
to  its  melting  point,  where  it  remains  stationary  for  some  time. 
The  melting  points  of  acids  of  various  strengths  are  as  follows: 

100  per  cent.,  16.75°  C.;  99.5  per  cent.,  15.65°;  99  per  cent.,  14.8°. 

For  Hanus's  solution  it  must  not  reduce  potassium  bichromate 
and  sulphuric  acid. 

Acetic  Anhydride. — Baker  and  Adamson's  C.  P.  or  Kahlbaum's 
"Essigsaures  Anhydrid." 

Alcohol. — Commercial  "Cologne  Spirits."  For  the  preparation 
of  alcohol  free  from  aldehyde  for  alcoholic  potash,  cologne  spirits 
are  treated  with  silver  oxide  as  follows:  one  and  one-half  grams 
of  silver  nitrate  are  dissolved  in  3  cc.  of  water,  added  to  one  liter  of 
alcohol  and  thoroughly  shaken;  three  grams  of  potassium  hydrate 
are  dissolved  in  15  cc.  warm  alcohol  and,  after  cooling,  added  to  the 
alcoholic  silver  nitrate  and  thoroughly  shaken  again,  best  in  a 
tall  bottle  or  cylinder.  The  silver  oxide  is  allowed  to  settle,  the 
clear  liquid  siphoned  off  and  distilled,  a  few  bits  of  pumice,  pre- 
pared by  igniting  it  and  immediately  quenching  under  water, 
being  added  to  prevent  bumping.  Alcohol  for  use  in  the  free 
acid  determination  is  prepared  by  placing  ten  to  fifteen  grams  of 
dry  sodium  carbonate  in  the  reagent  bottle,  taking  care  to  filter 
it  before  use. 

Alcohol,  Amyl. — Kahlbaum's  manufacture. 

i  Mcllhiney  et  al.,  J.  Am.Chem.  Soc.,  29,  1224  (1907). 


166  APPENDIX. 

Bromine. — The  commercial  article;  also  a  3  solution,  made  by 
dissolving  26.6  grams  bromine  in  one  liter  carbon  tetrachloride. 

Calcium  Chloride. — The  dry  and  also  the  crystallized  salt. 

Calcium  Sulphate. — Plaster  of  Paris. 

Carbon  Tetrachloride. — Baker  and  Adamson's  C.  P.  or  Kahl- 
baum  's  "  Tetrachlorkohlenstoff . ' ' 

Chloroform— Squibb 's,  U.  S.  P. 

Copper. — Copper  turnings  or  clippings,  used  for  the  generation 
of  nitric  oxide. 

Copper  Wire. — Cut  in  pieces  of  0.3  to  0.5  gram. 

Ether.— Squibb's,  U.  S.  P. 

Gasolene. — Gasolene,  86°  Baume". 

Hydrochloric  Acid,  C.  P.— Specific  gravity  1.2.  For  f  HC1 
dilute  thirty-nine  cubic  centimeters  of  the  above  acid  to  one  liter 
and  standardize. 

Iodine  Solution. — Fifty  grams  of  iodine  to  one  liter  of  alcohol. 
For  Hanus's  solution  dissolve  by  warming  13.2  grams  iodine  in 
one  liter  glacial  acetic  acid;  cool  and  add  three  cubic  centimeters 
of  bromine. 

Lead,  Precipitated. — Place  strips  of  zinc  in  the  solution  of  lead 
acetate  below.  When  the  precipitation  is  nearly  complete  the 
lead  is  washed  with  water,  alcohol,  and  ether,  and  dried  finally  in 
a  vacuum  desiccator. 

Lead  Acetate. — One  hundred  grams  of  the  salt  to  one  liter. 

Litmus  Paper. 

Mercuric  Chloride. — Sixty  grams  of  the  salt  to  one  liter  of  alcohol. 

Nitric  Acid. — Specific  gravity  1.34. 

Phenolphthalein. — One  gram  of  the  substance  to  five  hundred 
cubic  centimeters  of  alcohol. 

M eta-Phosphoric  Add. — A  saturated  solution  of  the  commercial 
"stick  phosphoric  acid"  in  absolute  alcohol. 

Potassium  Bichromate. — Dissolve  3.8747  grams  of  the  C.  P. 
salt  in  one  liter  of  water;  one  cubic  centimeter  is  equivalent  to 
0.01  gram  of  iodine.  The  solution  should  be  tested  against  iron 
wire  containing  a  known  percentage  of  iron. 

Potassium  Hydrate. — f:  Dissolve  thirty  grams  of  "potash 
by  alcohol"  in  one  liter  of  alcohol.  £:  Dissolve  ten  grams  of  ordi- 
nary "  stick  potash ' '  in  one  liter  of  water  and  dilute  to  proper 
strength.  The  solution  should  be  protected  by  stick  potash  from 
the  carbon  dioxide  in  the  air.  Ten  per  cent.:  Dissolve  one  hun- 


APPENDIX.  167 

dred  grams  of  "stick  potash"  in  eleven  hundred  cubic  centimeters 
of  alcohol. 

Potassium  lodate. — A  two  per  cent,  solution. 

Potassium  Iodide. — One  hundred  grams  of  the  commercial  salt 
are  dissolved  in  one  liter  of  water.  This  should  be  free  from  iodate, 
shown  by  yielding  no  coloration  when  acidified  with  strong  HC1. 

Silver  Nitrate.— Thirty  grams  to  one  liter  +  0.4  Cc.  HNO,. 

Sodium. 

Sodium  Chloride. — Ordinary  "coarse  fine"  salt  for  freezing 
mixtures. 

Sodium  Hydrate. — 36°  Baume*.  Dissolve  three  hundred  grams 
of  caustic  soda  in  one  liter  of  water. 

Sodium  Nitroprusside. — The  commercial  salt. 

Sodium  Thiosulphate.  —  y^-:  Dissolve  twenty-six  grams  of 
"sodium  hyposulphite"  in  one  liter  of  water;  the  addition  of  two 
grams  of  ammonium  carbonate  to  the  liter  is  said  by  Mohr  to 
improve  the  stability  of  the  solution. 

Starch  Solution. — Rub  up  in  a  mortar  one  gram  of  potato  starch 
with  ten  to  fifteen  cubic  centimeters  of  water,  pour  this  into  two 
hundred  cubic  centimeters  of  water  which  are  boiling  actively,  and 
continue  the  boiling  for  a  few  minutes. 

Sugar. — Ordinary  granulated  sugar. 

Sulphur. — A  1.5  per  cent,  solution  in  carbon  bisulphide. 

Sulphuric  Acid,  C.  P. — This  should  be  at  least  ninety-nine  and 
five-tenths  per  cent,  pure,  and  its  strength  be  determined  by  titra- 
tion,  as  one  hundred  per  cent,  and  ninety-four  and  three-tenths 
per  cent,  acid  have  the  same  specific  gravity,  1.8384.1 

Dilute. — One  part  acid  to  ten  parts  of  water. 

Nitrosulphuric  Acid,  for  the  Elaidin  Test. — A  liter  of  sulphuric 
acid  of  46°  Baume"  (1.47  specific  gravity)  is  prepared  by  diluting 
five  hundred  and  sixty  cubic  centimeters  commercial  sulphuric 
acid  to  one  liter;  a  few  drops  of  nitric  acid  are  added  and  nitric 
oxide  (generated  from  copper  and  nitric  acid)  passed  in  until  it 
is  saturated.  The  acid  is  then  cooled  in  ice-water  and  the  gas 
passed  in  until  it  is  saturated  at  0°  C.  This  is  called  Roth's  liquid. 

Tin  Tetrabromide. — This  is  prepared2  by  allowing  bromine  to 
fall  drop  by  drop  upon  granulated  tin  contained  in  a  dry  flask  im- 


i Richmond,  J.  Soc.  Chem.  Ind.,  9,  479  (1890). 
1  Allen,  Commercial  Organic  Analysis,  ii,  463. 


168  APPENDIX. 

mersed  in  cold  water  until  the  coloration  shows  bromine  to  be  in 
excess.  A  small  quantity  of  bromine  is  then  added  and  the  liquid 
diluted  with  three  to  four  times  its  volume  of  carbon  bisulphide. 

OILS    FOR  RAILROAD  USE. 

The  railroads  being  among  the  largest  users  of  oil, 
their  requirements  are  of  interest;  as  they  do  not 
differ  widely,  those  of  the  Philadelphia  and  Reading 
Railroad  will  serve  as  a  sample. 

Specifications  for   Lard  Oil. 

When  a  shipment  of  oil  is  received  a  sample  will  be  taken  at 
random  from  each  sixty  barrels  or  fraction  thereof,  and  forwarded 
to  the  Test  Department.  This  sample  will  be  examined  and  the 
entire  shipment  accepted  or  rejected  on  its  merits.  If  rejected  the 
shipment  will  be  returned  at  the  shipper's  expense. 

Two  grades  of  Lard  Oil  will  be  used,  "Prime"  and  "Extra  No. 
1";  the  former  for  burning  purposes  chiefly,  and  the  latter  as  a 
lubricant.  The  material  desired  under  this  specification  is  oil  from 
fresh  lard  of  corn-fed  hogs,  unmixed  with  other  oils.  It  should 
contain  the  least  possible  amount  of  free  acid,  and  from  October  1 
to  May  1  show  a  cold  test  not  higher  than  40°  F. 

PRIME  LARD  OIL. 

This  grade  of  oil  must  not  contain  admixtures  of  any  other  oils 
or  more  free  acid  than  is  neutralized  by  four  cubic  centimeters  of 
alkali,  as  described  below. 

Between  October  1  and  May  1  it  must  show  a  cold  test  below 
45°  F. 

When  tested  with  nitrate  of  silver,  as  described  below,  it  must 
not  show  any  coloration. 

EXTRA  No.  1  LARD  OIL. 

This  grade  of  oil  must  not  contain  admixtures  of  any  other  oils 
or  more  free  acid  than  is  neutralized  by  thirty  cubic  centimeters  of 
alkali,  as  described  below. 

Between  October  1  and  May  1  it  must  show  a  cold  test  below  45°  F. 

The  Cold  Test.— The  cold  test  is  made  as  follows: 


APPENDIX.  169 

About  two  ounces  of  oil  are  put  in  a  four-ounce  sample  bottle,  a 
thermometer  inserted,  and  the  oil  frozen  with  ice,  salt  being  used 
if  necessary.  When  the  oil  is  hard,  the  bottle  is  taken  from  the 
freezing  mixture  and  the  frozen  oil  stirred  thoroughly  with  the 
thermometer  until  it  will  flow.  The  reading  of  the  thermometer  is 
then  taken,  and  this  temperature  is  regarded  as  the  cold  test  of  the  oil. 
Free  Add  Test. — The  solutions  required  for  this  test  are  ninety- 
five  per  cent,  alcohol  neutralized  with  sodium  carbonate,  caustic 
potash  solution  of  such  a  strength  that  31.5  cubic  centimeters  of  it 
will  exactly  neutralize  five  cubic  centimeters  of  a  normal  solution 
of  sulphuric  acid  (forty-nine  grams  per  liter),  and  a  small  amount 
of  Phenolphthalein  dissolved  in  Alcohol,  and  rendered  neutral  with 
caustic  potash,  to  be  used  as  an  indicator. 

Now  weigh  or  measure  into  a  four-ounce  sample  bottle  8.9  grams 
of  the  oil  to  be  tested,  add  about  two  ounces  of  Alcohol,  warm  to 
about  150°  F.,  and  add  a  few  drops  of  the  Phenolphthalein. 

Then  run  in  the  caustic  potash  from  a  graduated  burette,  with 
frequent  shaking,  until  a  permanent  pink  color  remains  after  vigor- 
ous shaking.  When  this  point  is  reached  read  the  number  of  cubic 
centimeters  used. 

Nitrate  of  Silver  Test. — Solution  of  Nitrate  of  Silver  is  made  as 
follows: 

Nitrate  of  Silver,  1  gram;  Alcohol,  200  grams;  Ether,  40  grams. 
After  the  ingredients  are  dissolved  and  mixed,  allow  the  solution 
to  stand  in  a  bright  light  until  it  has  become  perfectly  clear;  it  is 
then  ready  for  use,  and  should  be  kept  in  a  dim  place,  and  tightly 
corked. 

Into  a  fifty  cubic  centimeter  test-tube  put  ten  cubic  centimeters 
of  the  oil  to  be  tested,  previously  filtered  through  washed  filter- 
paper.  Add  five  cubic  centimeters  of  the  above  solution,  shake 
thoroughly,  and  heat  in  a  vessel  of  boiling  water  fifteen  minutes 
with  occasional  shaking.  If  the  oil  is  satisfactory  it  will  show  no 
change  of  color  under  this  test. 

Specifications  for  Petroleum  Products. 

When  a  shipment  of  oil  is  received,  a  sample  shall  be  taken  at 
random  and  forwarded  to  the  Test  Department.  This  sample  will 
be  examined  and  the  entire  shipment  accepted  or  rejected  on  its 
merits.  If  rejected,  the  shipment  will  be  returned  at  the  shipper's 
expense. 


170  APPENDIX. 

150°  FIRE  TEST  OIL. 

This  grade  of  oil  shall  be  water-white  in  color,  showing  a  flash- 
ing point  not  below  130°  F.,  and  a  burning  point  not  below  151°. 
The  test  will  be  made  in  an  open  vessel  by  heating  the  oil  not  less 
than  ten  degrees  per  minute,  and  applying  the  test  flame  every 
seven  degrees,  beginning  at  123°.  The  gravity  may  be  from  46°  to 
50°  Baume\  Oil  will  not  be  received  which  is  cloudy  from  the 
presence  of  glue  or  suspended  matter  of  any  kind. 

300°  FIRE  TEST  OIL. 

This  grade  of  oil  shall  be  water-white  in  color,  show  a  flashing 
point  not  below  256°  F.,  and  a  burning  point  not  below  298°.  The 
test  will  be  made  in  an  open  vessel  by  heating  the  oil  not  less  than 
fifteen  degrees  per  minute,  and  applying  the  test  flame  every  seven 
degrees,  beginning  at  249°. 

When  heated  to  a  temperature  of  425°  and  held  there  for  five 
minutes,  the  oil  must  remain  clear  and  transparent,  showing  but  a 
slight  darkening  and  no  separation  of  flocculent  or  other  matter, — 
either  at  this  temperature  or  on  cooling. 

When  the  oil  is  cooled  to  the  temperature  of  32°,  and  held  there 
for  ten  minutes,  it  must  remain  clear  and  transparent,  showing  no 
cloudiness.  The  gravity  may  be  from  38°  to  42°  Baume*. 

Oil  will  not  be  received  which  is  cloudy  from  the  presence  of 
glue  or  suspended  matter  of  any  kind. 

CAR  OIL. 

This  grade  of  oil,  commonly  known  as  Well  Oil  or  Black  Oil, 
should  have  a  gravity  of  about  29°  Baume",  and  must  not  show  a 
flashing  point  below  325°  F.  The  test  will  be  made  in  an  open 
vessel  by  heating  the  oil  not  less  than  fifteen  degrees  per  minute, 
and  applying  the  test  flame  once  in  seven  degrees,  beginning  at  304°. 

Oil  received  during  the  months  of  August  and  September  must 
have  a  cold  test  not  above  15°  F.,  and  from  October  1  to  April  1,  a 
cold  test  not  above  5°  F.  when  determined  as  described  below. 

From  August  1  to  April  1,  at  80°  F.,  the  oil  must  show  a  vis- 
cosity not  lower  than  that  of  a  pure  cane  sugar  solution  containing 
eighty  grams  of  sugar  in  one  hundred  cubic  centimeters  of  the 
syrup,  and  at  150°  F.  a  viscosity  not  lower  than  that  of  a  pure 
cane  sugar  solution  containing  sixty-six  grams  of  sugar  in  one 
hundred  cubic  centimeters  of  the  syrup,  the  viscosity  of  the  sugai 
solution  being  taken  at  80°  F. 


APPENDIX.  171 

From  April  1  to  August  1,  at  80°  F.,  the  oil  must  show  a  vis- 
cosity not  lower  than  that  of  a  pure  cane  sugar  solution  containing 
eighty-eight  grams  of  sugar  in  one  hundred  cubic  centimeters  of 
the  syrup,  and  at  150°  F.  a  viscosity  not  lower  than  that  of  a  pure 
cane  sugar  solution  containing  sixty-eight  grams  of  sugar  in  one 
hundred  cubic  centimeters  of  the  syrup,  nor  higher  than  that  given 
by  a  pure  cane  sugar  solution  containing  seventy-five  grams  of 
sugar  in  one  hundred  cubic  centimeters  of  the  syrup,  the  viscosity 
of  the  sugar  solutions  being  taken  at  80°  F. 

The  oil  must  be  transparent  with  a  reddish-brown  or  greenish 
color,  free  from  lumps  or  specks. 

No  oil  will  be  accepted  which  shows  more  than  five  per  cent,  of 
flocculent  or  tarry  matter  settled  out  after  five  cubic  centimeters  of 
the  oil  have  been  mixed  with  ninety-five  cubic  centimeters  of  88° 
Gasolene,  and  allowed  to  stand  for  an  hour. 

CYLINDER  STOCK. 

This  grade  of  oil  shall  show  a  flashing  point  not  below  525°  F., 
and  a  burning  point  not  below  600°  F.  The  test  will  be  made  in  an 
open  vessel  by  heating  the  oil  not  less  than  twenty  degrees  per 
minute,  and  applying  the  test  flame  every  seven  degrees,  beginning 
at  504°. 

This  oil  must  flow  readily  at  60°  F.,  and  at  350°  F.  must  show 
a  viscosity  not  lower  than  that  of  a  pure  cane  sugar  solution  con- 
taining fifty-eight  grams  of  sugar  in  one  hundred  cubic  centimeters 
of  the  syrup,  the  viscosity  of  the  sugar  solution  being  taken  at 
80°  F. 

The  oil  must  be  transparent,  with  a  reddish-brown  or  greenish 
color,  free  from  lumps  or  specks. 

No  oil  will  be  accepted  which  shows  more  than  five  per  cent,  of 
flocculent  or  tarry  matter  settled  out  after  five  cubic  centimeters  of 
the  oil  have  been  mixed  with  ninety-five  cubic  centimeters  of  88° 
Gasolene,  and  allowed  to  stand  for  one  hour. 

Cold  Test. — About  two  ounces  of  oil  are  put  in  a  four-ounce 
sample  bottle,  a  thermometer  inserted,  and  the  oil  frozen  with  a 
mixture  of  ice  and  salt.  When  the  oil  is  hard  the  bottle  is  taken 
from  the  freezing  mixture  and  the  frozen  oil  stirred  thoroughly 
with  the  thermometer  until  it  will  flow.  The  reading  of  the  ther- 
mometer is  then  taken,  and  this  temperature  is  regarded  as  the 
cold  test  of  the  oil. 


172  APPENDIX. 

NOTE. — The  viscosity  tests  will  be  made  upon  the  Torsion  Vis- 
cosimeter. 

Manufacturers  not  having  this  instrument  may  submit  a  sample 
of  oil  to  the  Test  Department,  and  will  be  furnished  with  the  infor- 
mation necessary  to  standardize  the  viscosimeter  they  may  have 
in  use. 

Specifications  for  Compound  Oils. 

When  a  shipment  of  oil  is  received,  a  sample  shall  be  taken  at 
random  and  forwarded  to  the  Test  Department.  This  sample  will 
be  examined  and  the  entire  shipment  accepted  or  rejected  on  its 
merits.  If  rejected,  the  shipment  will  be  returned  at  the  shipper's 

expense. 

CYLINDER  OIL. 

This  oil  shall  consist  of  a  high-grade  cylinder  stock,  compounded 
with  not  less  than  twenty  per  cent,  by  weight  of  acidless  animal 
oil,  Tallow  or  Tallow  Oil  being  preferred. 

The  compounded  oil  shall  show  a  flashing  point  not  below  525° 
F.,  and  a  burning  point  not  below  600°.  The  test  will  be  made  in 
an  open  vessel  by  heating  the  oil  not  less  than  twenty  degrees  per 
minute,  and  applying  the  test  flame  every  seven  degrees,  beginning 
at  504°. 

This  oil  must  flow  readily  at  60°  F.,  and  at  a  temperature  of 
350°  F.  must  show  a  viscosity  not  lower  than  that  of  a  pure  cane 
sugar  solution  containing  fifty-eight  grams  of  sugar  in  one  hundred 
cubic  centimeters  of  the  syrup,  the  viscosity  of  the  sugar  solution 
being  taken  at  80°  F. 

The  oil  must  be  transparent,  with  a  reddish-brown  or  greenish 
color,  free  from  lumps  or  specks. 

No  oil  will  be  accepted  which  shows  more  than  five  per  cent,  of 
flocculent  or  tarry  matter  settled  out  after  five  cubic  centimeters 
of  the  oil  have  been  mixed  with  ninety-five  cubic  centimeters  of 
88°  Gasolene,  and  allowed  to  stand  for  one  hour. 

SIGNAL  OIL. 

This  grade  of  oil  shall  be  prime  white  in  color,  shall  contain  not 
less  than  forty  per  cent,  by  weight  of  Prime  Lard  Oil,  and  shall 
show  a  flashing  point  not  below  200°  F.,  and  a  burning  point  not 
above  300°.  The  test  will  be  made  in  an  open  vessel  by  heating 
the  oil  not  less  than  fifteen  degrees  per  minute,  and  applying  the 
test  flame  every  seven  degrees,  beginning  at  193°. 


APPENDIX.  173 

When  heated  to  a  temperature  of  450°,  and  held  there  for  five 
minutes,  the  oil  must  remain  clear  and  transparent,  showing  but  a 
slight  darkening  and  no  separation  of  flocculent  or  other  matter, 
either  at  this  temperature  or  on  cooling.  The  gravity  may  be  from 
31°  to  34°  Baume*. 

Oil  will  not  be  received  which  is  cloudy  from  the  presence  of 
glue  or  suspended  matter  of  any  kind. 

No.  1  ENGINE  OIL. 

This  oil  shall  consist  of  a  high  grade  of  mineral  oil,  compounded 
with  not  less  than  ten  per  cent,  by  weight  of  nearly  acidless  animal  oil. 

It  shall  show  a  gravity  of  about  29°  Baume*,  and  a  flashing 
point  not  below  325°  F.  The  test  will  be  made  in  an  open  vessel 
by  heating  the  oil  not  less  than  fifteen  degrees  per  minute,  and 
applying  the  test  flame  once  in  seven  degrees,  beginning  at  304°. 

Oil  received  during  the  months  of  August  and  September  must 
have  a  cold  test  not  above  15°  F.,  and  from  October  1  to  April  1  a 
cold  test  not  above  5°  F.,  when  determined  as  described  below. 

From  August  1  to  April  1,  at  80°  F.,  the  oil  must  show  a  vis- 
cosity not  lower  than  that  of  a  pure  cane  sugar  solution  containing 
eighty  grams  of  sugar  in  one  hundred  cubic  centimeters  of  the 
syrup,  and  at  150°  a  viscosity  not  lower  than  that  of  a  pure  cane 
sugar  solution  containing  sixty-six  grams  of  sugar  in  one  hundred 
cubic  centimeters  of  the  syrup,  the  viscosity  of  the  sugar  solution 
being  taken  at  80°  F. 

From  April  1  to  August  1,  at  80°  F.,  the  oil  must  show  a  vis- 
cosity not  lower  than  that  of  a  pure  cane  sugar  solution  containing 
eighty-eight  grams  of  sugar  in  one  hundred  cubic  centimeters  of 
the  syrup,  and  at  150°  F.  a  viscosity  not  lower  than  that  of  a  pure 
cane  sugar  solution  containing  sixty-eight  grams  of  sugar  in  one 
hundred  cubic  centimeters  of  the  syrup,  nor  higher  than  that  given 
by  a  solution  of  pure  cane  sugar  containing  seventy-five  grams  of 
sugar  in  one  hundred  cubic  centimeters  of  the  syrup,  the  viscosity 
of  the  sugar  solutions  being  taken  at  80°  F. 

The  oil  must  be  transparent,  with  a  reddish-brown  or  greenish 
color,  free  from  lumps  or  specks. 

No  oil  will  be  accepted  which  shows  more  than  five  per  cent, 
of  flocculent  or  tarry  residue  settled  out  after  five  cubic  centimeters 
of  the  oil  have  been  mixed  with  ninety-five  cubic  centimeters  of 
88°  Gasolene,  and  allowed  to  stand  for  an  hour. 


174  APPENDIX. 

No.  2  ENGINE  OIL. 

The  requirements  for  this  oil  are  identically  the  same  as  those 
for  No.  1  Engine  Oil,  with  the  following  exceptions: 

It  must  contain  not  less  than  twenty  per  cent,  by  weight  of 
nearly  acidless  animal  oil. 

From  October  1  to  April  1  the  cold  test  must  be  not  above  10° 
F.  when  determined  as  described  below. 

SCREW-CUTTING    OlL. 

This  oil  shall  consist  of  paraffine  oil  of  about  27°  Baume*  gravity, 
compounded  with  not  less  than  twenty-five  per  cent,  by  weight  of 
Fat  Oil,  Cotton-seed  preferred. 

The  compound  oil  shall  show  a  flashing  point  not  below  300° 
F.,  and  a  burning  point  not  above  425°.  The  test  will  be  made  in 
an  open  vessel  by  heating  the  oil  not  less  than  fifteen  degrees  per 
minute,  and  applying  the  test  flame  once  in  seven  degrees,  begin- 
ning at  276°. 

From  October  1  to  April  1  the  oil  must  have  a  cold  test  not  above 
15°  F.  when  determined  as  described  below. 

Cold  Test. — About  two  ounces  of  oil  are  placed  in  a  four-ounce 
sample  bottle,  a  thermometer  inserted,  and  the  oil  frozen  with  a 
mixture  of  ice  and  salt.  When  the  oil  is  hard,  the  bottle  is  taken 
from  the  freezing  mixture,  and  the  frozen  oil  stirred  thoroughly 
with  the  thermometer  until  it  will  flow.  The  reading  of  the  ther- 
mometer is  then  taken,  and  this  temperature  is  regarded  as  the 
cold  test  of  the  oil. 

NOTE. — The  viscosity  tests  will  be  made  upon  the  Torsion  Vis- 
cosimeter. 

Manufacturers  not  having  this  instrument  may  submit  a  sample 
of  oil  to  the  Test  Department,  and  will  be  furnished  with  the  infor- 
mation necessary  to  standardize  the  instrument  they  may  have  in  use. 

Specifications  for  Tallow. 

Tallow  to  be  used  for  cylinder  lubrication  should  be  rendered 
as  soon  as  possible  after  the  animal  is  killed,  in  order  to  have  the 
amount  of  free  acid  as  small  as  possible. 

Tallow  which  on  examination  is  found  to  contain  dirt  or  crack- 
lings disseminated  through  it,  or  which  has  a  layer  of  dirt  or  crack- 
lings in  the  bottom  of  the  barrel  more  than  an  eighth  of  an  inch 
thick,  will  be  rejected. 


APPENDIX.  175 

Tallow  will  not  be  accepted  which  has  more  free  acid  than  can 
be  neutralized  by  three  cubic  centimeters  of  the  alkali  solution 
used  for  this  determination  (p.  78),  or  which  contains  any  foreign 
substance  not  properly  belonging  to  tallow. 

Specifications  for  Transformer  Oil. 

Transformer  oils l  should  be  either  pure  mineral  or  rosin  oils  and 
be  free  from  water,  acid,  and  alkali. — Heated  in  Holde's  apparatus 
for  two  hours  at  170°  they  should  lose  less  than,  one  per  cent. 
(Holde's  apparatus  consists  of  a  copper  cup  55  mm.  in  diameter  and 
in  depth,  which  is  filled  to  within  2  cm.  of  the  top  and  heated  in  a 
glycerine  or  other  suitable  bath.)  The  viscosity  should  be  low,  less 
than  408  second  Saybolt  at  70°  F.  They  should  remain  liquid  at  0°  C. 
The  flash  point  should  be  not  less  than  190°  C.  in  the  open  tester. 

iHolde,  Schmiermittel  Untersuchung,  p.  66,  1905. 


INDEX 


Acid,  arachidic,  115. 
Acidity,  detection  of,  23,  78. 
Adulteration,  calculation  of,  62. 
Animal  oils,  test  for,  90. 
Antifluorescents,  detection  of,  43. 

Bach's  test,  77. 
Baudouin's  test,  76. 
Baume  hydrometer,  19. 
Bechi  test,  72. 
Benzine,  deodorized,  100. 
Black  oil,  151. 
Bromine  number,  63. 
Burning  oil  distillate,  99-101. 
oils,  13,  101. 

Canadol,  100. 

Caoutchouc,  43. 

Chilling  point,  39. 

Cholesterol,  melting  point  of,  92. 

esters,  melting  point  of,  92. 

test  for,  92. 
Cold  test,  38. 
Color  of  oils,  9. 

reactions,  72. 

Cotton-seed  oil  test  for,  74. 
Cymogene,  100. 

Danforth's  oil,  100. 

Degras,  141,  147. 

Determination  of  mineral  salts,  24. 

of  sulphur,  21. 

of  water,  24. 
Distillation  test,  20. 
Distilled  grease,  144. 
oleines,  144. 
stearines,  144. 
Drying  test,  81. 

Elaidin  test,  51. 
Evaporation  test,  37. 
Export  oil,  101. 


Fatty  oils,  test  for,  45. 
Fire  test,  burning  oils,  19. 

lubricating  oils,  41. 
Flash  point,  burning  oils,  13. 

conditions  influencing,  14. 
lubricating  oils,  40. 
test,  13. 

Fluorescence,  observation  of,  45. 
Foots,  149. 
Free  acid  test,  78. 
Freezing  mixtures,  39. 
Friction  machines,  46. 

tests,  46. 
Fuller's  grease,  150. 

Garbage  grease,  151. 
Gasolene,  100. 
Gumming  test,  45. 

Halphen's  test,  74. 
Hanus's  method,  56. 
Headlight  oil,  101. 
Heat  of  bromination  test,  55. 
Hexabromide  test,  105. 
Hubl's  method,  58. 

Iodine  number,  55. 

oxidized  oils,  63,  127. 

Kerosene,  101. 
Koettstorfer's  method,  65. 

Lanoline,  144. 

Liebermann-Storch  test,  120. 
Ligroine,  101. 
Livache  test,  81. 
Lubricants,  86. 

Lubricating  oil  distillate,  99,  101. 
oils,  26. 


Mackey's  apparatus,  78. 
Maumeng  test,  52. 


177 


178 


INDEX. 


McHhiney's  method,  63 

Mineral  salts,  effects  of,  in  burning 

oils,  24. 
sperm,  101. 
Moellon,  147. 

Naphtha,  100. 

distillate,  99. 
Nitro-benzene,  43. 

naphthalene,  43. 

Odor  of  oils,  9,  89. 
Oil,  almond,  113. 

arachis,  114. 

black,  151. 

castor,  112. 

Chinese  wood,  106. 

cocoanut,  129. 

cod,  133. 

corn,  108. 

cotton-seed,  109. 

earthnut,  114. 

elain,  138. 

horse,  135. 

Japanese  wood,  106. 

jaw,  87. 

lard,  135. 

linseed,  103. 

bleached,  105. 
boiled,  104. 

maize,  108. 

"melon,"  87. 

menhaden,  132. 

neat's-foot,  134. 

olive,  117. 

palm,  128. 

peanut,  114. 

poppy-seed,  107. 

"pulp,"  42. 

rape,  111. 

blown,  127. 

red,  138. 

rosin,  118. 

sesame*,  110. 

sod,  147. 

sperm,  139. 

sunflower,  108. 

tallow,  137. 

"thickener,  "42. 

transformer,  175. 

tung,  106. 


Oil,  whale,  133. 
Oils,  animal,  49. 

blown,  127. 

burning,  13,  101,  170. 

classification  of,  97. 

clock,  87. 

cylinder,  87,  101,  172. 

drying,  103. 

engine,  87,  101,  173. 

loom,  101. 

lubricating,  26,  87. 

machinery,  87. 

neutral,  101. 

non-drying,  113. 

oxidized,  iodine  number  of,  63. 

paraffine,  102. 

semi-drying,  108. 

spindle,  87,  101. 

vegetable,  49. 

watch,  87. 
Oil  foots,  149. 

Petroleum  ether,  100. 
Phytosterol,  melting  point  of,  92. 

esters,  melting  point  of,  92. 

test  for,  92. 
Prices  of  oils,  88. 

Reagents,  165. 

Renard's  test  for  rosin  oil,  120. 
Rhigolene,  100. 
Rosin,  grades  of,  122. 
spirits,  121. 

Saponification  value,  65. 

Sesame"  oil,  test  for,  76. 

Sherwood  oil,  100. 

Soap,  detection  of,  42. 

Sod  oil,  147. 

Specific  gravity,  19,  36,  49,  89. 

Specifications  for  oils,  86,  108. 

car  oil,  170. 

cylinder  oil,  171,  172. 
stock,  171. 

engine  oil,  173,  174. 

150°  fire  test,  170. 

300°  fire  test,  170. 

lard  oil,  168. 

screw-cutting  oil,  174, 

signal  oil,  172. 

tallow,  174. 


INDEX. 


179 


Specifications  for  transformer  oil,  175. 
Spontaneous  combustion  test,  78. 
Sulphur  in  oils,  21. 
Sulphuric  acid  test  for  burning  oils,  23. 

Tables:     I.,    flash   and   fire   test,    re- 
quirements, 153. 

II.,   flash  and   fire  test,  various 
oils,  154. 

III.,  Baumd,  degrees  and  specific 
gravity,  156. 

IV.,  specific  gravity  and  weight 
of  oils,  157. 

V.— VIII.,  comparison  of  viscosi- 
meters,  158-161. 

IX.,  constants  of  various  oils,  161. 

X.,  volumetric  factors,  162. 

XI.,  action  of  oils  upon  metals, 
162. 

XII.,    constants    of    fatty   acids 
from  various  oils,  163. 

XIII.,  bromine  addition  and  sub- 
stitution figures,  163. 

XIV.,      comparison      of      Hubl, 
Hanus,      and      Wijs      iodine 
values,  164. 
Test,  animal  oils,  90. 

Bach's,  77. 

Baudouin's,  76. 

Bechi,  72. 

Camoin's,  76. 

cold,  38. 

distillation,  20. 

drying,  81. 

elaidin,  51. 

evaporation,  37. 

fatty  oils,  45. 

fire,  19,  41. 

flash,  13,  40. 

free  acid,  78. 

gumming,  45. 


Test,  Halphen's,  74. 
Hanus's,  130. 
heat  of  bromination,  55. 
hexabromide,  105. 
Liebermann-S  torch,  120. 
Livache,  81. 
Maumend,  52. 
Renard,  120. 
soap,  42. 

spontaneous  combustion,  78. 
titer,  82. 
Valenta's,  50. 
vegetable  oils,  90. 

Tester,  covered,  15. 

Massachusetts,  18. 

New  York  State,  15. 

Tagliabue,  open,  18. 
Titer  test,  82. 
Turpentine,  122. 

wood,  126. 

Unknown  oil,  examination  of,  88. 
Unsaponifiable  oils,  detection  of,  68. 
examination  of,  70. 

Valenta  test,  50. 
Vegetable  oils,  test  for,  90. 
Viscosimeter,  Doolittle's,  33. 

Saybolt's"A,"27. 

Saybolt's"C,"29. 
Universal,  30. 

Traube's,  35. 

Viscosimetrical  tables,  158—161. 
Viscosity,  definition  of,  26. 

Water,  determination  of,  24. 
Westphal's  balance,  36. 
"White  Gelatin,  "42. 
Wool  fat,  141. 
grease,  141. 


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